Substituted pyridyl amine catalysts and processes for polymerizing and polymers

ABSTRACT

New ligands, compositions, metal-ligand complexes and arrays with pyridyl-amine ligands are disclosed that catalyze the polymerization of monomers into polymers. Certain of these catalysts with hafnium metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, isobutylene or styrene. Certain of the catalysts are particularly effective at polymerizing propylene to high molecular weight isotactic polypropylene in a solution process at a variety of polymerization conditions.

[0001] This application claims the benefit of U.S. Provisional PatentApplication No. 60/246,78 1, filed Nov. 7, 2000 and the benefit of U.S.Provisional Patent Application No. 60/301,666, filed Jun. 28, 2001, bothof which are incorporated herein by reference for all purposes.

FIELD OF THE INVENTION

[0002] The present invention relates to ligands, complexes, compositionsand/or catalysts that provide enhanced olefin polymerizationcapabilities based on a substituted pyridyl amine structure and hafnium.The invention also relates to methods of polymerization. The inventionalso relates to isotactic polypropylene and methods of preparingisotactic polypropylene.

BACKGROUND OF THE INVENTION

[0003] Ancillary (or spectator) ligand-metal coordination complexes(e.g., organometallic complexes) and compositions are useful ascatalysts, additives, stoichiometric reagents, monomers, solid stateprecursors, therapeutic reagents and drugs. Ancillary ligand-metalcoordination complexes of this type can be prepared by combining anancillary ligand with a suitable metal compound or metal precursor in asuitable solvent at a suitable temperature. The ancillary ligandcontains functional groups that bind to the metal center(s), remainassociated with the metal center(s), and therefore provide anopportunity to modify the steric, electronic and chemical properties ofthe active metal center(s) of the complex.

[0004] Certain known ancillary ligand-metal complexes and compositionsare catalysts for reactions such as oxidation, reduction, hydrogenation,hydrosilylation, hydrocyanation, hydroformylation, polymerization,carbonylation, isomerization, metathesis, carbon-hydrogen activation,carbon-halogen activation, cross-coupling, Friedel-Crafts acylation andalkylation, hydration, dimerization, trimerization, oligomerization,Diels-Alder reactions and other transformations.

[0005] One example of the use of these types of ancillary ligand-metalcomplexes and compositions is in the field of polymerization catalysis.In connection with single site catalysis, the ancillary ligand typicallyoffers opportunities to modify the electronic and/or steric environmentsurrounding an active metal center. This allows the ancillary ligand toassist in the creation of possibly different polymers. Group 4metallocene based single site catalysts are generally known forpolymerization reactions. See, generally, “Chemistry of CationicDicyclopentadienyl Group 4 Metal-Alkyl Complexes”, Jordan, Adv.Organometallic Chem., 1991, Vol. 32, pp. 325-153 and “StereospecificOlefin Polymerization with Chiral Metallocene Catalysts”, Brintzinger,et al., Angew. Chem. Int. Ed. Engl., 1995, Vol. 34, pp. 1143-1170, andthe references therein, all of which is incorporated herein byreference.

[0006] However, those of skill in the art of single site catalysisappreciate that there may be substantial differences in performancebetween different metal centers. For example, U.S. Pat. No . 5,064,802discloses a broad category of mono-cyclopentadienyl ligand catalystswith a broad disclosure of useful metals, and U.S. Pat. No. 5,631,391more specifically discloses that titanium metal centers offerperformance advantages with respect to the same or similar ligands.Additionally, Coates, et al., Angew. Chem. Int. Ed., 2000, vol. 39, pp.3626-3629 describes the unpredictable nature of olefin polymerizationcatalyst structure-activity relationships. Thus, references thatdescribe, for example, groups 3-13 and the lanthanides, for example inU.S. Pat. No. 6,103,657, are not of adequate performance indicators ofall that is within the scope of what is allegedly described. Moreover,as those of skill in the art appreciate, differences in ligandsubstituents typically polymerize different monomers at differentperformances under different polymerization conditions, and discoveringthose specifics remains a challenge.

[0007] One application for metallocene catalysts is producing isotacticpolypropylene. An extensive body of scientific literature examinescatalyst structures, mechanism and polymers prepared by metallocenecatalysts. See, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253-1345 and G. W. Coates, “Precise Control of PolyolefinStereochemistry Using Single-Site Metal Catalysts,” Chem. Rev. 2000,100, 1223-1252 and the references sited in these review articles. Seealso, U.S. Pat. No. 5,026,798 that reports a mono-cyclopentadienylmetallocene for the production of isotactic polypropylene. Isotacticpolypropylene has historically been produced with heterogeneouscatalysts that may be described as a catalyst on a solid support (e.g.,titanium tetrachloride and aluminum alkyls on magnesium dichloride).This process typically uses hydrogen to control the molecular weight andelectron-donor compounds to control the isotacticity. See also EP0622380, U.S. Patent No. 4,297,465, U.S. Patent No. 5,385,993 and U.S.Patent No. 6,239,236.

[0008] Given the extensive research activities with respect tometallocene catalysts, there is continued interested in the nextgeneration of non-cyclopentadienyl ligands for olefin polymerizationcatalysts providing attractive alternatives. See, e.g., “The Search forNew-Generation Olefin Polymerization Catalysts: Life beyondMetallocenes”, Gibson, et al., Angew. Chem. Int. Ed., 1999, vol. 38, pp.428-447; Organometallics 1999, 18, pp. 3649-3670. Recently, such systemshave been discovered, see, e.g., U.S. Pat. No. 6,103, 657 and U.S. Pat.No. 5,637,660. For isotactic polypropylene, bis-amide catalysts havebeen disclosed in U.S. Pat. No. 5,318,935 and amidinate catalysts havebeen disclosed in WO 99/05186. See also U.S. Pat. No. 6,214,939.

[0009] There remains a need for the discovery and optimization ofnon-cyclopentadienyl based catalysts for olefin polymerization, and inparticular for certain polymers, such as isotactic polypropylene andethylene-alpha-olefin copolymers. For a solution polymerizationmethodology, this need may be acute in view of the lack of versatilecatalysts for the preparation of isotactic polypropylene at commerciallyacceptable temperatures. Indeed, new polymer properties are disclosedherein for isotactic polypropylene, ethylene-styrene copolymers andethylene-isobutylene copolymers.

SUMMARY OF THE INVENTION

[0010] This invention discloses surprising enhanced catalyticperformances for olefin polymerization when certain combinations ofligands and hafnium metal precursors are employed. This invention alsodiscloses surprising enhanced catalytic performances for olefinpolymerization when certain metal complexes are employed in a catalyst,including 2,1 metal complexes and 3,2 metal complexes. In addition, someof the ligands employed herein are themselves novel.

[0011] In some embodiments, this invention discloses both the preferreduse of a hafnium metal center and certain pyridyl-amine ligands. Suchcombinations lead to new ligand-metal complexes, catalyst compositionsand processes for the polymerization of olefins, diolefins, or otherpolymerizable monomers. In particular, copolymers of ethylene andanother monomer may be prepared with controlled incorporation of theother monomer (e.g., 1-octene, isobutylene, or styrene) into the polymerbackbone. In some embodiments, this control is adjusted so that theolefin incorporation is considered to be high with respect to polymerscurrently known or commercially available. Also in particular, propylenemay be polymerized into very high molecular weight isotacticpolypropylene. Thus, polymers having novel, improved or desiredproperties may be prepared using the catalysts and processes of thisinvention.

[0012] More specifically, in some embodiments, the use of a hafniummetal has been found to be preferred as compared to a zirconium metalfor pyridyl-amine ligand catalysts. A broad range of ancillary ligandsubstituents may accommodate the enhanced catalytic performance. Thecatalysts in some embodiments are compositions comprising the ligand andmetal precursor, and optionally may additionally include an activator,combination of activators or activator package.

[0013] The invention disclosed herein additionally includes catalystscomprising ancillary ligand-hafnium complexes, ancillaryligand-zirconium complexes and optionally activators, which catalyzepolymerization and copolymerization reactions, particularly withmonomers that are olefins, diolefins or other unsaturated compounds.Zirconium complexes, hafnium complexes, compositions or compounds usingthe disclosed ligands are within the scope of this invention. Themetal-ligand complexes may be in a neutral or charged state. The ligandto metal ratio may also vary, the exact ratio being dependent on thenature of the ligand and metal-ligand complex. The metal-ligand complexor complexes may take different forms, for example, they may bemonomeric, dimeric or higher orders thereof.

[0014] For example, suitable ligands useful in this invention may becharacterized by the following general formula:

[0015] wherein R¹ is a ring having from 4-8 atoms in the ring generallyselected from the group consisting of substituted cycloalkyl,substituted heterocycloalkyl, substituted aryl and substitutedheteroaryl, such that R¹ may be characterized by the general formula:

[0016] where Q¹ and Q⁵ are substituents on the ring ortho to atom E,with E being selected from the group consisting of carbon and nitrogenand with at least one of Q¹ or Q⁵ being bulky (defined as having atleast 2 atoms). Q″_(q) represents additional possible substituents onthe ring, with q being 1, 2, 3, 4 or 5 and Q″ being selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

[0017] Also for example, in some embodiments, the ligands of theinvention may be combined with a metal precursor compound that may becharacterized by the general formula Hf(L)_(n) where L is independentlyselected from the group consisting of halide (F, Cl, Br, I), alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof, and optionally two L groups may be linked togetherin a ring structure. n is 1, 2, 3, 4, 5, or 6.

[0018] In another aspect of the invention, a polymerization process isdisclosed for monomers. The polymerization process involves subjectingone or more monomers to the catalyst compositions or complexes of thisinvention under polymerization conditions. The polymerization processcan be continuous, batch or semi-batch and can be homogeneous, supportedhomogeneous or heterogeneous. Another aspect of this invention relatesto arrays of ligands, metal precursors and/or metal-ligand complexes.These arrays are useful for the high speed or combinatorial materialsscience discovery or optimization of the catalyst compositions orcomplexes disclosed herein.

[0019] These catalysts comprising ancillary ligand-metal complexes orcompositions comprising metal precursors and ligands and, optionally,activators are particularly effective at polymerizing α-olefins (such aspropylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, andstyrene), copolymerizing ethylene with α-olefins (such as propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), andcopolymerizing ethylene with 1,1-disubstituted olefins (such asisobutylene). These compositions might also polymerize monomers thathave polar functionalities in homopolymerizations or copolymerizations.Also, diolefins in combination with ethylene and/or α-olefins or1,1-disubstituted olefins may be copolymerized. The new catalystcompositions can be prepared by combining a hafnium precursor with asuitable ligand and, optionally, an activator or combination ofactivators. This invention discloses a novel class of catalysts andimproved method for preparing isotactic polypropylene. The catalyst isuseful for polymerizing a wide variety of polymerizable monomers.

[0020] In particular, a method of producing isotactic polypropylene isin a solution process is disclosed and is surprisingly tunable. In oneaspect, the temperature of the solution polymerization process can beincreased, which generally decreases the molecular weight, butsurprisingly, while maintaining a relatively high isotacticity of thepolypropylene and while maintaining a relatively high melting point forthe polypropylene. In another aspect, the temperature of the solutionprocess can be increased without the molecular weight of thepolypropylene dropping so low to levels that are unacceptable forcertain commercial applications.

[0021] In certain aspects, it has been discovered that certain ligandscomplex to the metal resulting in novel complexes. In one aspect, the3,2 metal-ligand complexes of this invention may be generallycharacterized by the following formula:

[0022] where M is zirconium or hafnium;

[0023] R¹ and T are defined above;

[0024] J″′ being selected from the group of substituted heteroaryls with2 atoms bonded to the metal M, at least one of those atoms being aheteroatom, and with one atom of J″′ is bonded to M via a dative bond,the other through a covalent bond; and L¹ and L² are independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, ethers, thioethers and combinationsthereof; and optionally the L groups may be linked together in a ringstructure.

[0025] In another aspect, a solution process to prepare isotacticpolypropylene is provided comprising adding a catalyst and propylenemonomer to a reactor and subjecting the contents to polymerizationconditions, where the temperature of the solution process is at least110° C. and polypropylene is produced that has a weight averagemolecular weight of at least 100,000, without a drop off in tacticityvalue (i.e., crystallinity index).

[0026] Thus, it is a feature of this invention to use hafnium-ligandcomplexes as polymerization catalysts with enhanced performance.

[0027] It is an object of this invention to polymerize olefins andunsaturated monomers with hafnium-ligand complexes. It is also an objectof this invention to polymerize olefins and unsaturated monomers withcompositions including substituted pyridyl amine ligands and hafniummetal precursors.

[0028] It is still a further object of this invention to polymerizeolefins and unsaturated monomers with the hafnium-ligand complexes thatadditionally comprise an activator or combination of activators.

[0029] It is also an object of this invention to use non-metallocenegroup 4 complexes as polymerization catalysts for the production ofisotactic polypropylene.

[0030] It is a further object of this invention to polymerize olefinsand unsaturated monomers with a catalyst comprised of metal complexescomprising 3,2 ligands.

[0031] Further objects and aspects of this invention will be evident tothose of skill in the art upon review of this specification.

BRIEF DESCRIPTION OF THE DRAWINGS

[0032]FIG. 1 depicts Table 1, which lists compounds that may be usefulfor synthesizing the ligands in this invention.

[0033]FIG. 2 depicts Table 2, which lists other compounds that may beuseful for synthesizing the ligands in this invention.

[0034]FIG. 3 depicts Table 3, which shows the ligands and results fromexamples, below, using the Hf metal precursor.

[0035]FIG. 4 depicts Table 4, which shows the ligands and results fromcomparative examples, below, using the Zr metal precursor.

DETAILED DESCRIPTION OF THE INVENTION

[0036] The inventions disclosed herein include metal complexes andcompositions, which are useful as catalysts for polymerizationreactions.

[0037] As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

[0038] “Hydrocarbyl” refers to univalent hydrocarbyl radicals containing1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including branched or unbranched,saturated or unsaturated species, such as alkyl groups, alkenyl groups,aryl groups, and the like. “Substituted hydrocarbyl” refers tohydrocarbyl substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” referto hydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

[0039] The term “alkyl” is used herein to refer to a branched orunbranched, saturated or unsaturated acyclic hydrocarbon radical.Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl,i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

[0040] “Substituted alkyl” refers to an alkyl as just described in whichone or more hydrogen atom bound to any carbon of the alkyl is replacedby another group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

[0041] The term “heteroalkyl” refers to an alkyl as described above inwhich one or more hydrogen atoms to any carbon of the alkyl is replacedby a heteroatom selected from the group consisting of N, O, P, B, S, Si,Sb, Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

[0042] The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

[0043] “Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

[0044] The term “heterocycloalkyl” is used herein to refer to acycloalkyl radical as described, but in which one or more or all carbonatoms of the saturated or unsaturated cyclic radical are replaced by aheteroatom such as nitrogen, phosphorous, oxygen, sulfur, silicon,germanium, selenium, or boron. Suitable heterocycloalkyls include, forexample, piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

[0045] “Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

[0046] The term “aryl” is used herein to refer to an aromaticsubstituent, which may be a single aromatic ring or multiple aromaticrings that are fused together, linked covalently, or linked to a commongroup such as a methylene or ethylene moiety. The aromatic ring(s) mayinclude phenyl, naphthyl, anthracenyl, and biphenyl, among others. Inparticular embodiments, aryls have between 1 and 200 carbon atoms,between 1 and 50 carbon atoms or between 1 and 20 carbon atoms. In someembodiments herein, multi-ring moieties are substituents and in such anembodiment the multi-ring moiety can be attached at an appropriate atom.For example, “naphthal” can be 1-naphthyl or 2-naphthyl; “anthracenyl”can be 1-anthracenyl, 2-anthracenyl or 9-anthracenyl; and“phenanthrenyl” can be 1-phenanthrenyl, 2-phenanthrenyl,3-phenanthrenyl, 4-phenanthrenyl phenanthrenyl or 9-phenanthrenyl.

[0047] “Substituted aryl” refers to aryl as just described in which oneor more hydrogen atom bound to any carbon is replaced by one or morefunctional groups such as alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and both saturated and unsaturated cyclichydrocarbons which are fused to the aromatic ring(s), linked covalentlyor linked to a common group such as a methylene or ethylene moiety. Thecommon linking group may also be a carbonyl as in benzophenone or oxygenas in diphenylether or nitrogen in diphenylamine.

[0048] The term “heteroaryl” as used herein refers to aromatic orunsaturated rings in which one or more carbon atoms of the aromaticring(s) are replaced by a heteroatom(s) such as nitrogen, oxygen, boron,selenium, phosphorus, silicon or sulfur. Heteroaryl refers to structuresthat may be a single aromatic ring, multiple aromatic ring(s), or one ormore aromatic rings coupled to one or more non-aromatic ring(s). Instructures having multiple rings, the rings can be fused together,linked covalently, or linked to a common group such as a methylene orethylene moiety. The common linking group may also be a carbonyl as inphenyl pyridyl ketone. As used herein, rings such as thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues of these rings are defined by the term “heteroaryl.”

[0049] “Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

[0050] The term “alkoxy” is used herein to refer to the —OZ¹ radical,where Z¹ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

[0051] As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical,where each of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

[0052] As used herein the term “boryl” refers to the —BZ¹Z2 group, whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

[0053] As used herein, the term “phosphino” refers to the group —PZ¹Z²,where each of Z¹ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

[0054] As used herein, the term “phosphine” refers to the group:PZ¹Z²Z³, where each of Z¹, Z³and Z² is independently selected from thegroup consisting of hydrogen, substituted or unsubstituted alkyl,cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl,heteroaryl, silyl, alkoxy, aryloxy, amino and combinations thereof.

[0055] The term “amino” is used herein to refer to the group —NZ¹Z²,where each of Z¹ and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl and combinations thereof.

[0056] The term “amine” is used herein to refer to the group :NZ¹Z²Z³,where each of Z¹, Z² and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof

[0057] The term “thio” is used herein to refer to the group —SZ¹, whereZ¹ is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

[0058] The term “seleno” is used herein to refer to the group —SeZ¹,where Z¹ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl,substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof

[0059] The term “saturated” refers to lack of double and triple bondsbetween atoms of a radical group such as ethyl, cyclohexyl,pyrrolidinyl, and the like.

[0060] The term “unsaturated” refers to the presence one or more doubleand triple bonds between atoms of a radical group such as vinyl,acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.

[0061] Other abbreviations used herein include: “Pr^(i)” to refer toisopropyl; “Bu^(t)” to refer to tertbutyl; “Me” to refer to methyl; and“Et” to refer to ethyl.

[0062] Ligands

[0063] Suitable ligands useful in this invention can be characterizedbroadly as monoanionic ligands having an amine and a heteroaryl orsubstituted heteroaryl group. The ligand substituents for particularmonomers are detailed near the end of this section. The ligands of theinvention may be characterized by the following general formula:

[0064] wherein R¹ is generally selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl and combinations thereof. In many embodiments, R¹ is a ringhaving from 4-8 atoms in the ring generally selected from the groupconsisting of substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl and substituted heteroaryl, with R¹ being characterizedby the general formula:

[0065] where Q¹ and Q⁵ are substituents on the ring ortho to atom E,with E being selected from the group consisting of carbon and nitrogenand with at least one of Q¹ or Q⁵ being bulky (defined as having atleast 2 non-hydrogen atoms). Q¹ and Q⁵ are independently selected fromthe group consisting of alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, aryl, substituted aryl and silyl, but providedthat Q¹ and Q⁵ are not both methyl. Q″_(q) represents additionalpossible substituents on the ring, with q being 1, 2, 3, 4 or 5 and Q″being selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl,silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, andcombinations thereof T is a bridging group selected group consisting of—CR²R³— and —SiR²R³— with R² and R³ being independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.J″ is generally selected from the group consisting of heteroaryl andsubstituted heteroaryl, with particular embodiments for particularreactions being described herein.

[0066] In a more specific embodiment, suitable ligands useful in thisinvention may be characterized by the following general formula:

[0067] wherein R¹ and T are as defined above and each of R⁴, R⁵, R⁶ andR⁷ is independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. Optionally, anycombination of R¹, R², R³ and R⁴ may be joined together in a ringstructure.

[0068] In certain more specific embodiments, the ligands in thisinvention may be characterized by the following general formula:

[0069] wherein Q¹, Q⁵, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above.Q², Q³ and Q⁴are independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof.

[0070] In other more specific embodiments, the ligands of this inventionand suitable herein may be characterized by the following generalformula:

[0071] wherein R¹, R², R³, R⁴, R⁵, and R⁶ are as defined above. In thisembodiment the R⁷ substituent has been replaced with an aryl orsubstituted aryl group, with R¹⁰, R¹¹, R¹² and R¹³ being independentlyselected from the group consisting of hydrogen, halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³groups may be joined to form a fused ring system having from 3-50non-hydrogen atoms. R¹⁴ is selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof.

[0072] In still more specific embodiments, the ligands in this inventionmay be characterized by the general formula:

[0073] wherein R²-R⁶, R¹⁰-R¹⁴ and Q¹-Q⁵ are all as define above.

[0074] In certain embodiments, R² is preferably hydrogen. Alsopreferably, each of R⁴ and R⁵ is hydrogen and R⁶ is either hydrogen oris joined to R⁷ to form a fused ring system. Also preferred is where R³is selected from the group consisting of benzyl, phenyl, naphthyl,2-biphenyl, t-butyl, 2-dimethylaminophenyl (2-(NMe₂)—C₆H₄—),2-methoxyphenyl (2-MeO—C₆H₄—), anthracenyl, mesityl, 2-pyridyl,3,5-dimethylphenyl, o-tolyl and phenanthrenyl. Also preferred is whereR¹ is selected from the group consisting of mesityl, 4-isopropylphenyl(4-Pr^(i)—C₆H₄), napthyl, 3,5-(CF₃)₂-C₆H₃—, 2-Me-napthyl,2,6-(Pr^(i))₂-C₆H₃—, 2-biphenyl, 2-Me-4-MeO—C₆H₃—, 2-Bu^(t)-C₆H₄—,2,5-(Bu^(t))₂-C₆H₃—, 2-Pr^(i)—6-Me-C₆H₃—, 2-Bu^(t)-6-Me-C₆H₃—,2,6-Et₂-C₆H₃— or 2-sec-butyl-6-Et-C₆H₃—. Also preferred is where R⁷ isselected from the group consisting of hydrogen, phenyl, napthyl, methyl,anthracenyl, phenanthrenyl, mesityl, 3,5-(CF₃)₂—C₆H₃—, 2-CF₃—C₆H₄—,4-CF₃—C₆H₄—, 3,5-F₂—C₆H₃—, 4-F—C₆H₄—, 2,4-F₂—C₆H₃—, 4-(NMe₂)—C₆H₄—,3-MeO—C₆H₄—, 4-MeO—C₆H₄—, 3,5-Me₂-C₆H₃—, o-tolyl, 2,6-F₂—C₆H₃—, or whereR⁷ is joined together with R⁶ to form a fused ring system, e.g.,quinoline. In some preferred embodiment, R⁴, R⁵ and R⁶ are eachindependently selected from the group consisting of alkyl, aryl, halide,alkoxy, aryloxy, amino, and thio.

[0075] In some embodiments, Q¹ and Q⁵ are, independently, selected fromthe group consisting of —CH₂R¹⁵, —CHR¹⁶R¹⁷ and methyl, provided that notboth Q¹and Q⁵ are methyl. In these embodiments, R¹⁵ is selected from thegroup consisting of alkyl, substituted alkyl, aryl and substituted aryl.R¹⁶ and R¹⁷ are independently selected from the group consisting ofalkyl, substituted alkyl, aryl and substituted aryl; and optionally R¹⁶and R¹⁷ are joined together in a ring structure having from 3-50non-hydrogen atoms.

[0076] Also optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joinedto form a fused ring system having from 3-50 non-hydrogen atoms inaddition to the pyridine ring, e.g. generating a quinoline group. Inthese embodiments, R³ is selected from the group consisting of aryl,substituted aryl, heteroaryl, substituted heteroaryl, primary andsecondary alkyl groups, and —PY₂ where Y is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

[0077] Optionally within above formulas IV and V, R⁶ and R¹⁰ may bejoined to form a ring system having from 5-50 non-hydrogen atoms. Forexample, if R⁶ and R¹⁰ together form a methylene, the ring will have 5atoms in the backbone of the ring, which may or may not be substitutedwith other atoms. Also for example, if R⁶ and R¹⁰ together form anethylene, the ring will have 6 atoms in the backbone of the ring, whichmay or may not be substituted with other atoms. Substituents from thering can be selected from the group consisting of halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof.

[0078] Specific examples of ligands within the scope of these formulasinclude:

[0079] In certain embodiments, the ligands are novel compounds and thoseof skill in the art will be able to identify such compounds from theabove. One example of the novel ligand compounds, includes thosecompounds generally characterized by formula (III), above where R² isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, and substituted aryl;and R³ is a phosphino characterized by the formula —PZ¹Z², where each ofZ¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof. Particularlypreferred embodiments of these compounds include those where Z¹ and Z²are each independently selected from the group consisting of alkyl,substituted alkyl, cycloalkyl, heterocycloalkyl, aryl, and substitutedaryl; and more specifically phenyl; where Q¹, Q³, and Q⁵ are eachselected from the group consisting of alkyl and substituted alkyl andeach of Q² and Q⁴ is hydrogen; and where R⁴, R⁵, R⁶ and R⁷ are eachhydrogen.

[0080] Certain embodiments of these ligands are preferred for thepolymerization of certain monomers. In any of the above formulas I, II,III, IV or V, for the production of isotactic polypropylene it is anaspect of this invention that R² cannot be the same group as R³, leadingto a chiral center on the carbon atom from which R² and R³ stem. Thus,generally, R³ may be selected from the group consisting of hydrogen,halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof, but it has also been learnedthat for isotactic polypropylene production R³ is aryl, substitutedaryl, heteroaryl or substituted heteroaryl. In more specific embodimentsfor isotactic polypropylene production R³ is selected from the groupconsisting of benzyl, phenyl, naphthyl, 2-biphenyl,2-dimethylaminophenyl, 2-methoxyphenyl, anthracenyl, mesityl, 2-pyridyl,3,5-dimethylphenyl, o-tolyl, or phenanthrenyl. Also here, R¹ is selectedfrom the group consisting of 2,6-(Pr^(i))₂—C₆H₃—, 2-Pr^(i)—6-Me-C₆H₃—,2,6-Et₂-C₆H₃— or 2-sec-butyl-6-Et-C₆H₃—.

[0081] Also for isotactic polypropylene production it is preferred thatwithin formula A, above, it is currently preferred that Q¹ and Q⁵ arealkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, silyl,cycloalkyl, or substituted cycloalkyl, provided that Q¹ and Q⁵ are notboth methyl. Here also, Q¹ and Q⁵ can be, independently, selected fromthe group consisting of —CH₂R¹⁵, —CHR¹⁶R¹⁷ and methyl, provided that notboth Q¹ and Q⁵ are methyl. In a more specific embodiment for isotacticpolypropylene production, it is currently preferred that Q¹ and Q⁵ areboth isopropyl; or both ethyl; or both sec-butyl; or Q¹ is methyl and Q⁵is isopropyl; or Q¹ is ethyl and Q⁵ is sec-butyl. Even morespecifically, with these Q¹ and Q⁵ preferences, R¹ is either

[0082] with the above definitions of the variables applying.

[0083] For isotactic polypropylene production it is preferred R⁷ isaryl, substituted aryl, heteroaryl or substituted heteroaryl, and morespecifically R⁷ is phenyl, napthyl, mesityl, anthracenyl orphenanthrenyl. Thus, most preferably, formulas IV and V above apply toisotactic polypropylene production, with it currently being preferredthat R¹⁰, R¹¹, R¹², R¹³, are each hydrogen; or one or more of R¹⁰, R¹¹,R¹², R¹³ are methyl, fluoro, trifluoromethyl, methoxy, or dimethylamino;or where R¹⁰ and R¹¹ are joined to form a benzene ring and R¹² and R¹³are each hydrogen (thus forming a napthyl group with the existing phenylring).

[0084] Specific ligands that are preferred for the production ofcrystalline polypropylene are:

[0085] For the production of ethylene-styrene copolymers, there aredifferent preferences depending on the type of polymer that is desired.In some embodiments, it is preferred that the ligands of either offormulas II, III, IV or V is used, particularly with R⁷ selected fromthe group consisting of aryl, substituted aryl, heteroaryl, andsubstituted heteroaryl. Specific ligands that are preferred forethylene-styrene copolymer production are:

[0086] For the production of ethylene-1-octene copolymers, it ispreferred that the ligands of either of formulas II, III, IV or V isused, with either or both of R³ and/or R⁷ being independently selectedfrom the group consisting of aryl, substituted aryl, heteroaryl, andsubstituted heteroaryl. Specific ligands that are preferred forethylene-1-octene copolymer production are:

[0087] For the production of ethylene-isobutylene copolymers, it iscurrently preferred that R² and R³ are either both hydrogen or R² ishydrogen and R³ is aryl, substituted aryl or substituted alkyl. It isalso important for ethylene-isobutylene copolymerization that R⁷ ishydrogen. Specific ligands useful in this invention for the productionof ethylene-isobutylene copolymers include:

[0088] The ligands of the invention may be prepared using knownprocedures. See, for example, Advanced Organic Chemistry, March, Wiley,New York 1992 (4^(th) Ed.). Specifically, the ligands of the inventionmay be prepared using the two step procedure outlined in Scheme 1.

[0089] In Scheme 1, the * represents a chiral center when R² and R³ arenot identical; also, the R groups have the same definitions as above.Generally, R³M² is a nucleophile such as an alkylating or arylating orhydrogenating reagent and M² is a metal such as a main group metal, or ametalloid such as boron. The alkylating, arylating or hydrogenatingreagent may be a Grignard, alkyl, aryl-lithium or borohydride reagent.Scheme 1, step 2 first employs the use of complexing reagent.Preferably, as in the case of Scheme 1, magnesium bromide is used as thecomplexing reagent. The role of the complexing reagent is to direct thenucleophile, R³M², selectively to the imine carbon. Where the presenceof functional groups impede this synthetic approach, alternativesynthetic strategies may be employed. For instance, ligands whereR³=phosphino can be prepared in accordance with the teachings of U.S.Pat. No. 6,034,240 and U.S. Pat. No. 6,043,363. In addition,tetra-alkylhafnium compounds or tetra-substituted alkylhafnium compoundsor tetra-arylhafnium compounds or tetra-substituted arylhafniumcompounds may be employed in step 2, in accordance with the teachings ofU.S. Pat. No. 6,103,657, which is incorporated herein by reference.Scheme 2 further describes a synthesis process:

[0090] In scheme 2, h=1 or 2 and the bromine ions may or may not bebound to the magnesium. The effect of the complexation is to guide thesubsequent nucleophilic attack by R³M² to the imine carbon. Thuscomplexation may lead to a more selective reaction that may increase theyield of the desired ancillary ligands. Using this technique,selectivity is generally greater than about 50%, more preferably greaterthan about 70% and even more preferably greater than about 80%.Complexation may be particularly useful for the preparation of arrays ofancillary ligands of the type disclosed in the invention, where R³ is avariable in the preparation of the ancillary ligand array. As shown inScheme 2 by the *, where R² and R³ are different, this approach alsoleads to the formation of a chiral center on the ancillary ligands ofthe invention. Under some circumstances R³M² may be successfully addedto the imine in the absence the complexing reagent. Ancillary ligandsthat possess chirality may be important in certain olefin polymerizationreactions, particularly those that lead to a stereospecific polymer, see“Stereospecific Olefin Polymerization with Chiral MetalloceneCatalysts”, Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, Vol.34, pp. 1143-1170, and the references therein; Bercaw et al., J. Am.Chem. Soc., 1999, Vol. 121, 564-573; and Bercaw et al., J. Am. Chem.Soc., 1996, Vol. 118, 11988-11989; each of which is incorporated hereinby reference.

[0091] In the practice of high throughput methods or combinatorialmaterials science, introduction of diversity may be important indesigning libraries or arrays. The synthetic schemes discussed hereinwill allow those of skill in the art to introduce diversity on theligands, which may assist in optimizing the selection of a particularligand for a particular polymerization reaction. Step 1 (see Schemel)may be conducted with, for example, any combination of the pyridines andanilines shown in Tables 1 and 2 (shown in FIGS. 1 and 2, respectively).The compounds shown in Tables 1 and 2 are meant to be illustrative andnon-limiting.

[0092] Compositions

[0093] Once the desired ligand is formed, it may be combined with ametal atom, ion, compound or other metal precursor compound. In someapplications, the ligands of this invention will be combined with ametal compound or precursor and the product of such combination is notdetermined, if a product forms. For example, the ligand may be added toa reaction vessel at the same time as the metal or metal precursorcompound along with the reactants, activators, scavengers, etc.Additionally, the ligand can be modified prior to addition to or afterthe addition of the metal precursor, e.g. through a deprotonationreaction or some other modification.

[0094] For formulas I, II, III, IV and V, the metal precursor compoundsmay be characterized by the general formula Hf(L)_(n) where L isindependently selected from the group consisting of halide (F, Cl, Br,I), alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine,hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio,1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers,thioethers and combinations thereof, and optionally two or more L groupsmay be linked together in a ring structure. n is 1, 2, 3, 4, 5, or 6.The hafnium precursors may be monomeric, dimeric or higher ordersthereof. It is well known that hafnium metal typically contains someamount of impurity of zirconium. Thus, this invention uses as purehafnium as is commercially reasonable. Specific examples of suitablehafnium precursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂PH)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.Specific examples include HfCl₄(THF)₂, HfCl₄(SMe₂)₂ andHf(CH₂Ph)₂Cl₂(OEt₂).

[0095] For formulas IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is hafnium orzirconium and each L is independently selected from the group consistingof halide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof.Optionally two or more L groups may be linked together in a ringstructure. n is 4, typically. It is well known that hafnium metaltypically contains some amount of impurity of zirconium. Thus, thisinvention uses as pure hafnium or zirconium as is commerciallyreasonable. Specific examples of suitable hafnium and zirconiumprecursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂SiMe₃)₃Cl,Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂, Hf(NMe₂)₄, Hf(NEt₂)₄,and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄, Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄,Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl, Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂,Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂, Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂,Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.Specific examples include HfCl₄(THF)₂, HfCl₄(SMe₂)₂ andHf(CH₂Ph)₂Cl₂(OEt₂).

[0096] The ligand to metal precursor compound ratio is typically in therange of about 0.01:1 to about 100:1, more preferably in the range ofabout 0.1:1 to about 10:1.

[0097] Metal-Ligand Complexes

[0098] This invention, in part, relates to new metal-ligand complexes.Generally, the ligand is mixed with a suitable metal precursor compoundprior to or simultaneously with allowing the mixture to be contactedwith the reactants (e.g., monomers). When the ligand is mixed with themetal precursor compound, a metal-ligand complex may be formed, whichmay be a catalyst or may need to be activated to be a catalyst. Themetal-ligand complexes discussed herein are referred to as 2,1 complexesor 3,2 complexes, with the first number representing the number ofcoordinating atoms and second number representing the number of anionicsites on the ligand. The 2,1 complexes therefore have two coordinatingatoms and a single anionic charge. Other embodiments of this inventionare those complexes that have a general 3,2 coordination scheme to ametal center, with 3,2 referring to a ligand that occupies threecoordination sites on the metal and two of those sites being anionic andthe remaining site being a neutral Lewis base type coordination.

[0099] Looking first at the 2,1 metal-ligand complexes, the metal-ligandcomplexes may be characterized by the following general formula:

[0100] wherein T, J″, R¹, L and n are as defined previously; and x is 1or 2. The J″ heteroaryl may or may not datively bond, but is drawn asbonding. More specifically, the metal-ligand complexes may becharacterized by the formula:

[0101] wherein R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are as defined previously;and x is 1 or 2. In one preferred embodiment x=1 and n=3. Additionally,Lewis base adducts of these metal-ligand complexes are also within thescope of the invention, for example, ethers, amines, thioethers,phosphines and the like are suitable as Lewis bases.

[0102] More specifically, the metal-ligand complexes of this inventionmay be characterized by the general formula:

[0103] wherein the variables are generally defined above. Thus, e.g.,Q², Q³, Q⁴, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to form afused ring system having from 3-50 non-hydrogen atoms in addition to thepyridine ring, e.g. generating a quinoline group; also, optionally, anycombination of R², R³ and R⁴ may be joined together in a ring structure;Q¹ and Q⁵ are selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,provided that Q¹ and Q⁵ are not both methyl; and each L is independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof; andoptionally two L groups may be linked together in a ring structure; n is1, 2, 3, 4, 5, or 6; and x=1 or 2.

[0104] In other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

[0105] wherein the variables are generally defined above.

[0106] In still other embodiments, the 2,1 metal-ligand complexes ofthis invention can be characterized by the general formula:

[0107] wherein the variables are generally defined above. The morespecific embodiments of the metal-ligand complexes of formulas VI, VII,VIII, IX and X are explained above with regard to the specificsdescribed for the ligands and metal precursors.

[0108] Lewis base adducts of these complexes are also suitable, forexample, ethers, amines, thioethers, phosphines and the like aresuitable as Lewis bases (note the definition of L).

[0109] Turning to the 3,2 metal-ligand complexes of this invention, themetal-ligand complexes in this aspect of this invention may be generallycharacterized by the general formula:

[0110] where M is zirconium or hafnium;

[0111] R¹and T are defined above;

[0112] J″ being selected from the group of substituted heteroaryls with2 atoms bonded to the metal M, at least one of those 2 atoms being aheteroatom, and with one atom of J″′ is bonded to M via a dative bond,the other through a covalent bond; and L¹ and L² are independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno,phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates,carbonates, nitrates, sulphates, and combinations thereof; andoptionally the L groups may be linked together in a ring structure.

[0113] More specifically, the 3,2 metal-ligand complexes of thisinvention may be characterized by the general formula:

[0114] where M is zirconium or hafnium;

[0115] T, R¹, R⁴, R⁵, R₆, L¹ and L² are defined above; and

[0116] E″ is either carbon or nitrogen and is part of an cyclic aryl,substituted aryl, heteroaryl, or substituted heteroaryl group.

[0117] Even more specifically, the 3,2 metal-ligand complexes of thisinvention may be characterized by the general formula:

[0118] where M is zirconium or hafnium; and

[0119] T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, L¹ and L² are definedabove.

[0120] Still even more specifically, the 3,2 metal-ligand complexes ofthis invention may be characterized by the general formula:

[0121] where M is zirconium or hafnium; and

[0122] T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹ andL² are defined above.

[0123] The more specific embodiments of the metal-ligand complexes offormulas XI, XII, XIII and XIV are explained above with regard to thespecifics described for the ligands and metal precursors. Lewis baseadducts of these complexes are also suitable, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.

[0124] In addition, preferences for the substituents on the ligands forproduction of the particular polymers discussed above (e.g., isotacticpolypropylene) apply to the metal-ligand complexes just described. Forisotactic polypropylene it is currently preferred that M is hafnium,although this preference is only slight as compared to zirconium. By“slight” here, it is meant that zirconium metal based polymerization ofpropylene for isotactic polypropylene shows similar tacticity control ascompared to hafnium metal based polymerization, however, the hafniumbased catalysts tend to show better polymerization activity andperformance overall.

[0125] For isotactic polypropylene production, it is currently preferredthat L¹ and L² are the same and selected from the group consisting ofalkyl and dialkyl amino, more specifically from the group consisting ofmethyl and dimethylamino.

[0126] As above, for production of isotactic polypropylene, R² and R³are not the same group, leading to a chiral center on the carbon atomfrom which R² and R³ stem. In more specific embodiments, R² is hydrogen.In more specific embodiments for isotactic polypropylene production R³is selected from the group consisting of hydrogen, halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof. In more specific embodiments for isotacticpolypropylene production R³ is aryl, substituted aryl, heteroaryl orsubstituted heteroaryl. In more specific embodiments for isotacticpolypropylene production R³ is selected from the group consisting ofbenzyl, phenyl, 2-biphenyl, 2-dimethylaminophenyl, 2-methoxyphenyl,anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl andphenanthrenyl.

[0127] In the above formulas, R¹⁰, R¹¹, R¹² and R¹³ are independentlyselected from the group consisting of hydrogen, halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³groups may be joined to form a fused ring system having from 3-50non-hydrogen atoms. Particular embodiments include, for example, forisotactic polypropylene production, it is currently preferred that R¹⁰,R¹¹, R¹², R¹³, are each hydrogen; or one or more of R¹⁰, R¹¹, R¹², R¹³are methyl, fluoro, trifluoromethyl, methoxy, or dimethylamino; or whereR¹⁰ and R¹¹ are joined to form a benzene ring and R¹² and R¹³ are eachhydrogen (thus forming a napthyl group with the existing phenyl ring).

[0128] Specific 2,1 and 3,2 metal complexes that are useful for theproduction of isotactic polypropylene include:

[0129] For the production of ethylene-styrene copolymers, there aredifferent preferences depending on the type of polymer that is desired.In some embodiments, it is preferred that the above formulas forcomplexes are used, particularly with R⁷ selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl. Specific 2,1 and 3,2 complexes that are preferred forethylene-styrene copolymer production include:

[0130] For the production of ethylene-1-octene copolymers, it ispreferred that the metal complexes of the above general formulas areused, with either or both of R³ and/or R⁷ being independently selectedfrom the group consisting of aryl, substituted aryl, heteroaryl, andsubstituted heteroaryl. Specific 2,1 and 3,2 metal complexes that arepreferred for ethylene-1-octene copolymer production include:

[0131] In addition, Lewis base adducts of the metal-ligand complexes inthe above formulas are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

[0132] The metal-ligand complexes can be formed by techniques known tothose of skill in the art, such as combinations of metal precursors andligands under conditions to afford complexation. In some embodiments,R¹⁴ is hydrogen and the metal-ligand complexes are formed by ametallation reaction (in situ or not) as shown below in

[0133] In scheme 3, R¹⁴ is hydrogen (but see above for the fulldefinition of R¹⁴ in other embodiments of this invention). Themetallation reaction to convert the 2,1 complex on the left to the 3,2complex on the right can occur via a number of mechanisms, likelydepending on the substituents chosen for L¹, L² and L³ and the othersubstituents such as Q¹-Q⁵, R²-R⁶, R¹⁰ to R₁₃. In one embodiment, whenL¹, L² and L³ are each N(CH₃)₂, the reaction can proceed by heating the2,1 complex to a temperature above about 100° C. In this embodiment, itis believed that L¹ and L² remain N(CH₃)₂ in the 3,2 complex. In anotherembodiment when L¹, L² and L³ are each N(CH₃)₂, the reaction can proceedby adding a group 13 reagent (as described below) to the 2,1 complex ata suitable temperature (such as room temperature). Preferably the group13 reagent for this purpose is di-isobutyl aluminum hydride,tri-isobutyl aluminum or trimethyl aluminum. In this embodiment, L¹ andL² are typically converted to the ligand (e.g., alkyl or hydride)stemming from the group 13 reagent (e.g., from trimethyl aluminum, L¹and L² are each CH₃ in the 3,2 complex). The 2,1 complex in scheme 3 isformed by the methods discussed above.

[0134] In an alternative embodiment possibly outside the scope of scheme3, for isotactic polypropylene production, it is currently preferredthat R1 ¹⁴ is either hydrogen or methyl.

[0135] Various references disclose metal complexes that may appear to besimilar; see for example, U.S. Pat. No. 6,103, 657 and U.S. Pat. No.5,637,660, both of which are incorporated herein by reference for allpurposes. However, certain embodiments of the invention herein provideunexpectedly improved polymerization performance (e.g., higher activityand/or higher polymerization temperatures and/or higher comonomerincorporation) relative to the embodiments disclosed in thosereferences. In particular, as shown in certain of the examples herein,the activity of the hafnium metal catalysts is far superior to that ofthe zirconium catalysts. Indeed, it also appears as if the zirconiummetal centered catalysts have inferior performance with respect toincorporation of comonomer into an ethylene/comonomer type copolymer,especially for 1-octene, isobutylene and styrene comonomers.

[0136] The ligands, complexes or catalysts may be supported on anorganic or inorganic support. Suitable supports include silicas,aluminas, clays, zeolites, magnesium chloride, polyethyleneglycols,polystyrenes, polyesters, polyamides, peptides and the like. Polymericsupports may be cross-linked or not. Similarly, the ligands, complexesor catalysts may be supported on similar supports known to those ofskill in the art. In addition, the catalysts of this invention may becombined with other catalysts in a single reactor and/or employed in aseries of reactors (parallel or serial) in order to form blends ofpolymer products.

[0137] Polymerization Activators/Additives

[0138] The metal-ligand complexes and compositions are active catalyststypically in combination with a suitable activator, combination ofactivators, activating technique or activating package, although some ofthe ligand-metal complexes may be active without an activator oractivating technique. Broadly, the activator(s) may comprise alumoxanes,Lewis acids, Bronsted acids, compatible non-interfering activators andcombinations of the foregoing. These types of activators have beentaught for use with different compositions or metal complexes in thefollowing references, which are hereby incorporated by reference intheir entirety: U.S. Pat. Nos. 5,599,761, 5,616,664, 5,453,410,5,153,157, 5,064,802, and EP-A-277,004. In particular, ionic or ionforming activators are preferred.

[0139] Suitable ion forming compounds useful as an activator in oneembodiment of the present invention comprise a cation that is a Bronstedacid capable of donating a proton, and an inert, compatible,non-interfering, anion, A⁻. Preferred anions are those containing asingle coordination complex comprising a charge-bearing metal ormetalloid core. Mechanistically, said anion should be sufficientlylabile to be displaced by olefinic, diolefinic and unsaturated compoundsor other neutral Lewis bases such as ethers or nitrites. Suitable metalsinclude, but are not limited to, aluminum, gold and platinum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions that comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

[0140] Preferably such activators may be represented by the followinggeneral formula:

(L*—H)_(d) ⁺(A^(d−))

[0141] wherein, L* is a neutral Lewis base; (L*—H)+is a Bronsted acid;A^(d−) is a non-interfering, compatible anion having a charge of d−, andd is an integer from 1 to 3. More preferably A^(d−) corresponds to theformula: [M′³⁺Q_(h)]^(d−) wherein h is an integer from 4 to 6; h−3=d; M′is an element selected from Group 13 of the Periodic Table of theElements; and Q is independently selected from the group consisting ofhydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, andsubstituted-hydrocarbyl radicals (including halidesubstitutedhydrocarbyl, such as perhalogenated hydrocarbyl radicals), said Q havingup to 20 carbons. In a more preferred embodiment, d is one, i.e., thecounter ion has a single negative charge and corresponds to the formulaA⁻.

[0142] Activators comprising boron or aluminum which are particularlyuseful in the preparation of catalysts of this invention may berepresented by the following general formula:

[L*—H]⁺[JQ₄]⁻

[0143] wherein: L* is as previously defined; J is boron or aluminum; andQ is a fluorinated C₁₋₂₀ hydrocarbyl group. Most preferably, Q isindependently selected from the group selected from the group consistingof fluorinated aryl group, especially, a pentafluorophenyl group (i.e.,a C₆F₅ group) or a 3,5-bis(CF₃)₂C₆H₃ group. Illustrative, but notlimiting, examples of boron compounds which may be used as an activatingcocatalyst in the preparation of the improved catalysts of thisinvention are tri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethylanilinium tetra-(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammoniumtetrakis(pentafluorophenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl) borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, tri(secbutyl)ammoniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl) borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate andN,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate;dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl) borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl) borate; and tri-substituted phosphoniumsalts such as:

[0144] triphenylphospnonium tetrakis(pentafluorophenyl) borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;and N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Preferred [L*—H]+cations areN,N-dimethylanilinium and tributylammonium. Preferred anions aretetrakis(3,5-bis(trifluoromethyl)phenyl)borate andtetrakis(pentafluorophenyl)borate. In some embodiments, the mostpreferred activator is PhNMe₂H⁺B(C₆F₅)₄ ⁻.

[0145] Other suitable ion forming activators comprise a salt of acationic oxidizing agent and a non-interfering, compatible anionrepresented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e)

[0146] wherein: Ox^(e+) is a cationic oxidizing agent having a charge ofe+; e is an integer from 1 to 3; and A^(d−), and d are as previouslydefined. Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

[0147] Another suitable ion forming, activating cocatalyst comprises acompound that is a salt of a carbenium ion or silyl cation and anon-interfering, compatible anion represented by the formula:

ĉ⁺A⁻

[0148] wherein: ĉ⁺ is a C₁₋₁₀₀ carbenium ion or silyl cation; and A⁻ isas previously defined. A preferred carbenium ion is the trityl cation,i.e. triphenylcarbenium. The silyl cation may be characterized by theformula Z¹Z²Z³Si⁺ cation, where each of Z¹, Z², and Z³ is independentlyselected from the group consisting of alkyl, substituted alkyl,cycloalkyl, heterocycloalkyl, heterocyclic, aryl, substituted aryl,heteroaryl, substituted heteroaryl and combinations thereof. In someembodiments, a most preferred activator is Ph₃C⁺B(C₆F₅)₄ ⁻.

[0149] Other suitable activating cocatalysts comprise a compound that isa salt, which is represented by the formula (A*^(+a))_(b)(Z*J*_(j))^(−c)_(d) wherein A* is a cation of charge +a; Z* is an anion group of from 1to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, furthercontaining two or more Lewis base sites; J* independently eachoccurrence is a Lewis acid coordinated to at least one Lewis base siteof Z*, and optionally two or more such J* groups may be joined togetherin a moiety having multiple Lewis acidic functionality; j is a numberform 2 to 12; and a, b, c, and d are integers from 1 to 3, with theproviso that a×b is equal to c×d. See, WO 99/42467, which isincorporated herein by reference. In other embodiments, the anionportion of these activating cocatalysts may be characterized by theformula ((C₆F₅)₃M″″—LN—M″″(C₆F₅)₃)⁻ where M″″ is boron or aluminum andLN is a linking group, which is preferably selected from the groupconsisting of cyanide, azide, dicyanamide and imidazolide. The cationportion is preferably a quaternary amine. See, e.g., LaPointe, et al.,J. Am. Chem. Soc. 2000, 122, 9560-9561, which is incorporated herein byreference.

[0150] In addition, suitable activators include Lewis acids, such asthose selected from the group consisting of tris(aryl)boranes,tris(substituted aryl)boranes, tris(aryl)alanes, tris(substitutedaryl)alanes, including activators such as tris(pentafluorophenyl)borane.Other useful ion forming Lewis acids include those having two or moreLewis acidic sites, such as those described in WO 99/06413 or Piers, etal. “New Bifunctional Perfluoroaryl Boranes: Synthesis and Reactivity ofthe ortho-Phenylene-Bridged Diboranes 1,2-[B(C₆F₅)₂]₂C₆X₄(X=H, F)” J.Am. Chem. Soc., 1999, 121, 3244-3245, both of which are incorporatedherein by reference. Other useful Lewis acids will be evident to thoseof skill in the art. In general, the group of Lewis acid activators iswithin the group of ion forming activators (although exceptions to thisgeneral rule can be found) and the group tends to exclude the group 13reagents listed below. Combinations of ion forming activators may beused.

[0151] Other general activators or compounds useful in a polymerizationreaction may be used. These compounds may be activators in somecontexts, but may also serve other functions in the polymerizationsystem, such as alkylating a metal center or scavenging impurities.These compounds are within the general definition of “activator,” butare not considered herein to be ion-forming activators. These compoundsinclude a group 13 reagent that may be characterized by the formulaG¹³R′_(3-p)D_(p) where G¹³ is selected from the group consisting of B,Al, Ga, In and combinations thereof, p is 0, 1 or 2, each R′ isindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, heterocyclic and combinationsthereof, and each D is independently selected from the group consistingof halide, hydride, alkoxy, aryloxy, amino, thio, phosphino andcombinations thereof. In other embodiments, the group 13 activator is anoligomeric or polymeric alumoxane compound, such as methylalumoxane andthe known modifications thereof. In other embodiments, a divalent metalreagent may be used that is defined by the general formulaM′R′_(2-p)D_(p) and p′ is 0 or 1 in this embodiment and R′ and D are asdefined above. M′ is the metal and is selected from the group consistingof Mg, Ca, Sr, Ba, Zn, Cd and combinations thereof. In still otherembodiments, an alkali metal reagent may be used that is defined by thegeneral formula M″R′ and in this embodiment R¹ is as defined above. M″is the alkali metal and is selected from the group consisting of Li, Na,K, Rb, Cs and combinations thereof. Additionally, hydrogen and/orsilanes may be used in the catalytic composition or added to thepolymerization system. Silanes may be characterized by the formulaSiR′_(4-q)D_(q) where R′ is defined as above, q is 1, 2, 3 or 4 and D isas defined above, with the proviso that there is at least one D that isa hydride.

[0152] The molar ratio of metal:activator (whether a composition orcomplex is employed as a catalyst) employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:10 to 1:1. In a preferred embodiment of the invention mixtures ofthe above compounds are used, particularly a combination of a group 13reagent and an ion-forming activator. The molar ratio of group 13reagent to ion-forming activator is preferably from 1:10,000 to 1000:1,more preferably from 1:5000 to 100: 1, most preferably from 1:100 to100:1. In a preferred embodiment, the ion forming activators arecombined with a tri-alkyl aluminum, specifically trimethylaluminum,triethylaluminum, tri-n-octylaluminum, or triisobutylaluminum or with adi-alkyl aluminum hydride such as di-isobutyl aluminum hydride. A mostpreferred combination is about 1 equivalent of N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, and 5-30 equivalents of a Group 13reagent. For ethylene-isobutylene copolymerization the group 13 reagentshould be present in at least an amount that is 0.1 equivalents of themetal (e.g., the metal presecur compound) and preferably in an amountthat is between 1 and 10 equivalents of the metal.

[0153] In other applications, the ligand will be mixed with a suitablemetal precursor compound prior to or simultaneous with allowing themixture to be contacted to the reactants. When the ligand is mixed withthe metal precursor compound, a metal-ligand complex may be formed,which may be a catalyst. In connection with the metal-ligand complex anddepending on the ligand or ligands chosen, the metal-ligand complex maytake the form of dimers, trimers or higher orders thereof or there maybe two or more metal atoms that are bridged by one or more ligands.Furthermore, two or more ligands may coordinate with a single metalatom. The exact nature of the metal-ligand complex(es) or compound(s)formed depends on the chemistry of the ligand and the method ofcombining the metal precursor and ligand, such that a distribution ofmetal-ligand complexes may form with the number of ligands bound to themetal being greater or less than the number of equivalents of ligandsadded relative to an equivalent of metal precursor.

[0154] Monomers/Polymers

[0155] The compositions, complexes and/or catalysts of this inventionare particularly effective at polymerizing α-olefins (such as propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene),copolymerizing ethylene with α-olefins (such as propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), andcopolymerizing ethylene with 1,1-disubstituted olefins (such asisobutylene). These compositions might also polymerize monomers thathave polar functionalities in homopolymerizations or copolymerizationsand/or homopolymerize 1,1-disubstituted olefins. Also, diolefins incombination with ethylene and/or α-olefins or 1,1-disubstituted olefinsmay be copolymerized. The new catalyst compositions can be prepared bycombining a metal precursor with a suitable ligand and, optionally, anactivator or combination of activators.

[0156] In general monomers useful herein may be olefinically orunsaturated monomers having from 2 to 20 carbon atoms either alone or incombination. Generally, monomers may include olefins, diolefins andunsaturated monomers including ethylene and C₃ to C₂₀ α-olefins such aspropylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene,1-norbornene, styrene and mixtures thereof, additionally,1,1-disubstituted olefins, such as isobutylene, 2-methyl-1-butene,2-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-hexene,3-trimethylsilyl-2-methyl-1-propene,α-methyl-styrene, either alone orwith other monomers such as ethylene or C₃ to C₂₀ α-olefins and/ordiolefins. The α-olefins listed above may be polymerized in astereospecific manner e.g. to generate isotactic or syndiotactic orhemiisotactic polypropylene. Additionally the α-olefins may bepolymerized to produce a polymer with differing tacticity sequenceswithin the polymer chain, such as polypropylene containing atactic andisotactic sequences within the same polymer chain. These definitions areintended to include cyclic olefins. Diolefins generally comprise1,3-dienes such as (butadiene), substituted 1,3-dienes (such asisoprene) and other substituted 1,3-dienes, with the term substitutedreferring to the same types of substituents referred to above in thedefinition section. Diolefins also comprises 1,5-dienes and othernon-conjugated dienes. The styrene monomers may be unsubstituted orsubstituted at one or more positions on the aryl ring. The use ofdiolefins in this invention is typically in conjunction with anothermonomer that is not a diolefin. In some embodiments, acetylenicallyunsaturated monomers may be employed.

[0157] More specifically, it has been found that the catalysts of thepresent invention are particularly active for certain monomers,particularly α-olefins. Thus, the catalysts of the present invention mayprovide higher comonomer incorporation for copolymers of ethylene andco-monomers having three or more carbon atoms.

[0158] In addition, the catalysts of the present invention maypolymerize vinyl chloride alone (e.g., in a homopolymerization) or withother monomers (such as ethylene or C₃ to C₂₀ α-olefins). Furthermore,vinyl monomers with functional groups may also be polymerized alone(e.g., in a homopolymerization) or with other monomers (such as ethyleneor C₃ to C₂₀ α-olefins). Such functional group containing vinyl monomerscan be characterized by the general formula H₂C═CH—FG, where FG is thefunctional group that contains at least one heteroatom (using theprevious definition) or halogen (e.g., Cl, F, Br, etc.). Functionalmonomers include C₁-C₂₀ acrylates, C₁-C₂₀ methacrylates, C₁-C₂₀vinylacetates, acrylic acid, methacrylic acid, maleic anhydride, vinylacetate, vinyl ethers, acrylonitrile, acrylamide, vinyl chloride andmixtures thereof.

[0159] Novel polymers, copolymers or interpolymers may be formed havingunique physical and/or melt flow properties. Such novel polymers can beemployed alone or with other polymers in a blend to form products thatmay be molded, cast, extruded or spun. End uses for the polymers madewith the catalysts of this invention include films for packaging, trashbags, bottles, containers, foams, coatings, insulating devices andhousehold items. Also, such functionalized polymers are useful as solidsupports for organometallic or chemical synthesis processes.

[0160] More specifically, the catalysts of this invention have preparednovel copolymers of ethylene and isobutylene. These novel polymers havehigh molecular weight combined with high incorporation of isobutylene.Others have broadly claimed such copolymers. See e.g., U.S. Pat. Nos.5,866,665 and 5,763,556, which are both incorporated herein byreference. However, the combination of these properties has not beenpreviously exemplified and is commercially promising. More specifically,the novel copolymers have a number average molecular weight of at least50,000 and a weight percent incorporation of isobutylene of at leastabout 30 wt. %.

[0161] Also, it has been found that the catalytic performance at hightemperature of particular catalysts of the present invention for thepolymerization of olefins in general, including the co-polymerization ofethylene and α-olefins, is unexpectedly good. In particular, it has beenfound that varying the ligand substituents (R and Q groups) discussedherein allows one to increase the polymerization performance and polymermolecular weight for olefin polymerizations at high temperatures,particularly for polymerization temperatures above 120° C. Inparticular, when R³ is aryl or substituted aryl, the high temperaturepolymerization catalytic performance is improved compared to when R³ ishydrogen or alkyl. Also, the steric bulk of the R¹ and R⁷ groups canaffect polymeization performance. In particular, improved hightemperature polymerization performance is observed when Q¹ and Q⁵ areboth not hydrogen.

[0162] It has been found that particular catalysts of the presentinvention co-polymerize ethylene and styrene (or substituted styrenes),forming ethylene-styrene copolymers. In particular, it has been foundthat varying the ligand substituents (R and Q groups) discussed hereinallows one to vary the ratio of styrene to ethylene incorporated in thecopolymer, and the ethylene-styrene copolymerization activity and Mw ofthe resulting ethylene-styrene copolymer. In particular, when R⁷ is arylor substituted aryl, the ratio of styrene to ethylene incorporated inthe copolymer is significantly higher than when R⁷ is hydrogen or alkyl.The higher level of styrene incorporation when R⁷ is aryl or substitutedaryl is unexpected.

[0163] The α-olefins listed above may be polymerized in a stereospecificmanner e.g. to generate isotactic or syndiotactic or hemiisotacticpoly-α-olefins. Additionally the α-olefins may be polymerized to producea polymer with differing tacticity sequences within the polymer chain,such as polypropylene containing atactic and isotactic sequences withinthe same polymer chain. The stereoregularity may be interrupted bystereoerrors, in particular isolated stereoerrors have been observed,which is an indication of enantiomorphic side control. Also regioerrorsmight be present in the isotactic polypropylene polymer as it isdescribed in the literature. In particular isolated 2-1 insertions maybe observed. (see, e.g., Resconi et al., “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev. 2000, 100,1253-1345).

[0164] More specifically, it has been found that particular catalysts ofthe present invention polymerize propylene to isotactic or crystallinepolypropylene, forming polymers with novel properties. Thispolymerization activity for isotactic polypropylene has surprisingperformance in a solution process. In particular, it has been found thatvarying the R and Q groups discussed herein allows one to vary thecrystallinity index of the crystalline polypropylene formed. In general,reducing the steric bulk of the R¹ group results in a polymer having alower crystallinity index, such that when Q¹ and Q⁵ are both methyl,tacticity may be insufficient to provide a crystalline polymer. Also,the steric bulk of the R³ and R⁷ group can affect the crystallinityindex.

[0165] The isotactic polypropylene polymers formed from these catalystsin a solution polymerization process have a crystallinity index ofbetween about 0.35 and about 0.95, more specifically between about 0.65and 0.95 and in some embodiments preferably above about 0.8, under thepolymerization conditions employed. The crystallinity index isdetermined using FTIR as is known to those of skill in the art andcalibrated based on a relative scale. In one embodiment, thecrystallinity index value can be determined using commercially availableFTIR equipment (such as a Bruker Equinox 55 with an IR Scope II inreflection mode using Pike MappIR software). The crystallinity index isobtained from the ratio of band heights at 995 cm⁻¹ and 972 cm⁻¹.Atactic polypropylene has a ratio of band heights or crystallinity indexof 0.2. Greater than 98% isotactic polypropylene has a crystallinityindex ratio of greater than 0.95. Generally, the amount of error incrystallinity index measurements is ±0.05. Polymer blends of variouscompositions show a linear relationship between % isotacticity andcrystallinity index. See, for example, J. P. Luongo, J. Appl. Polym.Sci., 3 (1960) 302-309 and T. Sundell, H. Fagerholm, H. Crozier, Polymer37 (1996) 3227-3231, each of which is incorporated herein by reference.

[0166] As those of skill in the art will recognize, isotacticity canalso be represented by percent pentads (% mmmm) as determined by ¹³C NMRspectroscopy. Proton decoupled ¹³C NMR spectroscopy can be performedusing commercially available equipment (such as a Bruker 300 MHz at 100°C. probe temperature) to determine the degree of tacticity as % mmmmpentads (for assignment of ¹³C signals see the review Brintzinger H. H.et al., Angew. Chem. Int. Ed. Eng. 1995, 34, 1143, which is incorporatedherein by reference). For example, a 15-30 mg polymer sample isdissolved in a 1:1 mixture Of C₂D₂Cl₄ and C₂Cl₄ by heating the sample toca. 100° C. The % mmmm is determined by the ratio of peak integral from23.5 to 21.5 ppm and peak integral 23.5 to 19 ppm. Proton decoupled ¹³CNMR spectroscopy can be also performed to determine the frequency of andnature of stereo errors and regioerrors.

[0167] In addition, the melting point of the crystalline polypropyleneis generally in the range of from about 115° C. to about 160° C., morespecifically between about 120° C. and 155° C., and in some embodimentspreferably above about 135° C. Melting points are determined bydifferential scanning calorimetry, as is known in the art (see also theexample section, herein). Surprisingly, the tacticity level and meltingpoint are relatively level throughout different polymerizationtemperatures.

[0168] The weight average molecular weight of the crystallinepolypropylene according to this application ranges from about 15,000 toabout 4,500,000 and for some embodiments more specifically between about50,000 to about 500,000 for the polymerization condition of apolymerization temperature at or above about 110° C. The polydispersityof the crystalline polypropylene of this invention (M_(w)/M_(n)) isgenerally about 2.5 or lower and in alternative embodiments is betweenabout 2.0 and 3.5. Molecular weight and polydispersity index isdetermined according to method known to those of skill in the art,based, generally on polystyrene standards. As those of skill in the artwill recognize, error in molecular weight measurements can range from10-20%.

[0169] Novel polymers, copolymers or interpolymers may be formed havingunique physical and/or melt flow properties. Polymers that can beprepared according to the present invention include propylene copolymerswith at least one C₄-C₂₀ α-olefin, particularly 1-butene, 1-hexene,4-methyl-1-pentene and 1-octene. The copolymers of propylene with atleast one C₄-C₂₀ α-olefin comprise from about 0.1 wt. % higher olefin toabout 60 wt. % higher olefin, more specifically from about 0.2 wt. %higher olefin to about 50 wt. % higher olefin and still morespecifically from about 2 wt. % higher olefin to about 30 wt. % higherolefin. For certain embodiments of this invention, crystallinecopolymers include those of propylene and a comonomer selected from thegroup consisting of ethylene, 1-butene, 1-hexene, and 1-octene comprisefrom about 0.2 to about 30 wt. % comonomer, more specifically from about1 to about 20 wt. % comonomer, even more specifically from about 2 toabout 15 wt. % comonomer and most specifically from about 5 to about 12wt. % comonomer.

[0170] The novel polymers (such as isotactic polypropylene) disclosedherein can be employed alone or with other natural or synthetic polymersin a blend. Such other natural or synthetic polymers can be polyethylene(including linear low density polyethylene, low density polyethylene,high density polyethylene, etc.), atactic polypropylene, nylon, EPDM,ethylene-propylene elastomer copolymers, polystyrene (includingsyndiotactic polystryene), ethylene-styrene copolymers and terpolymersof ethylene-styrene and other C₃-C₂₀ olefins (such as propylene).

[0171] Melt flow rate (MRF) for polypropylene and copolymer of propyleneand one or more C₄-C₂₀ α-olefins is measured according to ASTM D-1238,condition L (2.16 kg, 230° C.). In some embodiments of this invention,the MFR is in the range of 0.005-1,000, more specifically 0.01-500 andeven more specifically 0.1-100. Flex modulus for polypropylene andcopolymer of propylene and one or more C₄-C₂₀ α-olefins is measuredaccording to ASTM D-790. In some embodiments of this invention, the flexmodulus ranges from 20,000-400,000 psi, more specifically from20,000-300,000 psi and even more specifically from 100,000-200,000 psi.Notch izod impact for polypropylene and copolymer of propylene and oneor more C₄-C₂₀ α-olefins is measured according to ASTM D-256A. In someembodiments of this invention, the notch izod impact ranges from 0.1 tono break in ft-lbs/in.

[0172] The novel polypropylene and copolymer of propylene and one ormore C₄-C₂₀ α-olefins disclosed in the present invention are useful fora wide variety of applications, including films (such as blown and castfilm, clarity film and multi-layer films), thermoforming (such as cups,plates, trays and containers), injection moulding, blow-moulding, foams(such as structural foams), pipe (such as potable water pipe and highpressure pipe), automotive parts, and other applications that will beevident to those of skill in the art.

[0173] Melt strength (measured in cN) and melt drawability (measured inmm/s) tests are conducted by pulling (“taking-up”) strands of the moltenpolymers or blends at constant acceleration until breakage occurs. Anexperimental set-up comprises a capillary rheometer and a Rheotensapparatus as a take-up device. The molten strands are drawn uniaxiallyto a set of accelerating nips located 100 mm below the die. The forcerequired to uniaxially extend the strands is recorded as a function ofthe take-up velocity or the nip rolls. In the case of polymer meltsexhibiting draw resonance (indicated by the onset of a periodicoscillation of increasing amplitude in the measured force profile), themaximum force and wheel velocity before the onset of draw resonance aretaken as the melt strength and melt drawability, respectively. In theabsence of draw resonance, the maximum force attained during testing isdefined as the melt strength and the velocity at which breakage occursis defined as the melt drawability. These tests are typically run underthe following conditions: Mass flow rate 1.35 grams/min Temperature 190°C. Equilibration time at 190° C. 10 minutes Die 20:1 (with entranceangle of approximately 45 degrees) Capillary length 41.9 mm Capillarydiameter 2.1 mm Piston diameter 9.54 mm Piston velocity 0.423 mm/s Shearrate 33.0 s⁻¹ Draw-down distance (die exit to take-up 100 mm sheels)Cooling conditions Ambient air Acceleration 2.4 mm/s²

[0174] For some aspects of the present invention the novel polymers areuseful to produce foams having improved properties. For foams and otherapplications requiring melt strength, the MFR is typically in the rangeof 0.1-10, more specifically in the range of 0.3-3 and most specificallyin the range of 0.5-2. The melt strength is typically greater than 5 cN,more specifically greater than 9 cN and most specifically greater than12 cN. The drawability is typically greater than 15 mm/sec, morespecifically greater than 25 mm/sec and most specifically greater than35 mm/sec.

[0175] In some aspects of the present invention, the novel polymersdisclosed herein are useful for a wide variety of applications wherecertain optical properties are beneficial. Gloss is measured accordingto ASTM D-1746. Haze is measured according to ASTM D-1003 and clarity ismeasured according to ASTM D-2457. The novel polymers disclosed hereinin some aspects are films having haze of less than 10%. In additionfilms having clarity of greater than 91% may be beneficially obtained.

[0176] Polymerization Systems

[0177] Polymerization can be carried out in the Ziegler-Natta orKaminsky-Sinn methodology, including temperatures of from −100° C. to300° C. and pressures from atmospheric to 3000 atmospheres. Suspension,solution, slurry, gas phase or high-pressure polymerization processesmay be employed with the catalysts and compounds of this invention. Suchprocesses can be run in a batch, semi-batch or continuous mode. Examplesof such processes are well known in the art. A support for the catalystmay be employed, which may be inorganic (such as alumina, magnesiumchloride or silica) or organic (such as a polymer or cross-linkedpolymer). Methods for the preparation of supported catalysts are knownin the art. Slurry, suspension, gas phase and high-pressure processes asknown to those skilled in the art may also be used with supportedcatalysts of the invention.

[0178] Other additives that are useful in a polymerization reaction maybe employed, such as scavengers, promoters, modifiers and/or chaintransfer agents, such as hydrogen, aluminum alkyls and/or silanes.

[0179] As discussed herein, catalytic performance can be determined anumber of different ways, as those of skill in the art will appreciate.Catalytic performance can be determined by the yield of polymer obtainedper mole of metal complex, which in some contexts may be considered tobe activity. Table 3 (FIG. 3) and Table 4 (FIG. 4) display the resultsof ethylene-1-octene copolymerizations using ancillary ligands of theinvention in combination with hafnium and zirconium precursors,respectively. In the case of zirconium, Table 4 illustrates that theyield of copolymer obtained from the experiments is the highest when thezirconium precursor (Zr(CH₂C₆H₅)₄) is employed without the use of anancillary ligand (Table 4 in FIG. 4; Cell A3: 369 mg). This illustratesthat the presence of the ancillary ligand may not necessarily enhancethe catalytic activity of the zirconium metal center. In the case ofhafnium, the yields are unexpected high. In contrast to zirconium, theyield of copolymer obtained when the hafnium precursor (Hf(CH₂C₆H₅)₄) isemployed without the use of an ancillary ligand is very low (Table 3 inFIG. 3; Cell A3: 47 mg).

[0180] Another measure of catalyst polymerization performance isco-monomer incorporation. As is well known in the art, many ethylenecopolymers are prepared using ethylene and at least one other monomer.These copolymers or higher order polymers in some applications requirehigher amounts of additional co-monomer(s) than have been practical withknown catalysts. Since ethylene tends to be the most reactive monomer,obtaining higher co-monomer incorporations is a benefit that is examinedfor polymerization catalysts. Two useful co-monomers are 1-octene andstyrene. This invention offers the possibility of higher incorporationof co-monomers such as 1-octene and styrene. As shown herein, theethylene/1-octene copolymers obtained from the combination of ancillaryligands and zirconium precursors all possess lower weight % 1-octenevalues (<11 wt. %) (Table 4 in FIG. 4), than the weight % 1-octenevalues for the ethylene/1-octene copolymers obtained from thecombination of ancillary ligands and hafnium precursors.

[0181] The results of the ethylene-1-octene copolymerizations usingancillary ligands of the invention in combination with a hafnium metalprecursor are surprising (Table 3 in FIG. 3). In contrast to zirconium,the yield of copolymer obtained when the hafnium precursor(Hf(CH₂C₆H₅)₄) is employed without the use of an ancillary ligand isvery low (cell A3: 47 mg). Surprisingly, in the presence of certainancillary ligands, the yields of copolymers obtained are enhanceddramatically relative to cell A3. In addition, the copolymers obtainedtypically possess higher wt. % 1-octene values relative to the valuesshown in Table 4. Additionally the wt. % 1-octene values for thecopolymers obtained span a wider range (<10 wt. % to 23 wt. %). Incontrast to Table 4, the results in Table 3 illustrate the ability ofthe ancillary ligand to tailor the catalytic performance of the hafniummetal center, both in terms of catalytic activity and the ability toincorporate 1-octene.

[0182] Tables 5 and 5a display the results of ethylene-styrenecopolymerizations using ancillary ligands of the invention incombination with hafnium and zirconium precursors. The results in Tables5 and 5a illustrate that certain combinations of ancillary ligands withhafnium precursors are more productive in the copolymerization ofethylene with styrene than are combinations of the same ancillaryligands with zirconium precursors. Additionally the results illustratecombinations of ancillary ligands with hafnium precursors to producecopolymers with a higher styrene incorporation (wt % styrene by NMR inTable 5 and mol % styrene by FTIR in Table 5a) than the styreneincorporation in the products produced by the combinations of the sameancillary ligands with zirconium precursors.

[0183] As stated herein, a solution process is specified for certainbenefits, with the solution process being run at a temperature above 90°C., more specifically at a temperature above 100° C., further morespecifically at a temperature above 110° C. and even further morespecifically at a temperature above 130° C. Suitable solvents forpolymerization are non-coordinating, inert liquids. Examples includestraight and branched-chain hydrocarbons such as isobutane, butane,pentane, isopentane, hexane, isohexane, heptane, octane, Isopar-E® andmixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perhalogenated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, chlorobenzene, and aromatic and alkylsubstituted aromaticcompounds such as benzene, toluene, mesitylene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene,styrene, divinylbenzene, allylbenzene, and vinyltoluene (including allisomers alone or in admixture). Mixtures of the foregoing are alsosuitable.

[0184] In some embodiments, a solution process is specified forcrystalline polypropylene production. The solution process to prepareisotactic polypropylene comprises adding a catalyst and propylenemonomer to a reactor and subjecting the contents to polymerizationconditions, such that polypropylene is obtained that has a crystallinityindex value that does not vary by more than about 0.1, when thetemperature of the solution process is varied from a temperature below90° C. to a temperature above 100° C. In some embodiments in thissection, the lower temperature is between about 70° C. and about 90° C.(or between about 75° C. and about 95° C. or between about 80° C. andabout 95° C.) and the higher temperature is between about 100° C. and110° C. (or between about 105° C. and about 115° C. or between about 100° C. and about 115° C.). In this context, the solution process can berun at a temperature and pressure that produce a desired product, butgenerally, the solution process temperature is above 100° C. and morespecifically above 110° C., while maintaining a high crystallinity indexvalue and high molecular weight. This solution polymerization processalso maintains the melting point of the polypropylene, such that it doesnot vary by more than 10° C., when the temperature of the solutionprocess is varied from a temperature below 90° C. to a temperature above100° C. In this context, the solution process can be run at atemperature and pressure that produce a desired product, but generally,the solution process temperature is above 100° C. and more specificallyabove 110° C., while maintaining a melting point above 135° C. (and ifdesired below about 155° C.). Also, in this solution process, theprocess temperature may be at least 110° C. while producingpolypropylene that has a weight average molecular weight of at least100,000, more preferably at least about 300,000. In alternativeembodiments the stated properties of the polymer are maintained when thetemperature of the solution process is varied from a temperature belowabout 95° C. to a temperature above 105° C. or from a temperature below85° C. to a temperature above 105° C. As with the above, thesealternative embodiments have a lower temperature limit of about 70° C.and an upper temperature limit of about 115° C. The polypropyleneproperties are made in a process that does not require separation orfractionation of a product into component products (such as separationof atactic polypropylene from crystalline polypropylene, as is known inthe art). Thus, in addition, the properties are measured on the bulksample. Otherwise, the solution process may be run in accord withmethods known to those of skill in the art.

[0185] Combinatorial Methodology

[0186] The ligands, metal-ligand complexes and compositions of thisinvention can be prepared and tested for catalytic activity in one ormore of the above reactions in a combinatorial fashion. Combinatorialchemistry generally involves the parallel or rapid serial synthesisand/or screening or characterization of compounds and compositions ofmatter. U.S. Pat. Nos. 5,985,356, 6,030,917 and WO 98/03521, all ofwhich are incorporated herein by reference, generally disclosecombinatorial methods. In this regard, the ligands, metal-ligandcomplexes or compositions may be prepared and/or tested in rapid serialand/or parallel fashion, e.g., in an array format. When prepared in anarray format, ligands, metal-ligand complexes or compositions may betake the form of an array comprising a plurality of compounds whereineach compound can be characterized by any of the above general formulas(i.e., I, A, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII orXIV). An array of ligands may be synthesized using the proceduresoutlined previously. The array may also be of metal precursor compounds,the metal-ligand complexes or compositions characterized by thepreviously described formulae and/or description. Typically, each memberof the array will have differences so that, for example, a ligand oractivator or metal precursor or R group in a first region of the arraymay be different than the ligand or activator or metal precursor or Rgroup in a second region of the array. Other variables may also differfrom region to region in the array.

[0187] In such a combinatorial array, typically each of the plurality ofcompositions or complexes has a different composition or stoichiometry,and typically each composition or complex is at a selected region on asubstrate such that each compound is isolated from the othercompositions or complexes. This isolation can take many forms, typicallydepending on the substrate used. If a flat substrate is used, there maysimply be sufficient space between regions so that there cannot beinterdiffusion between compositions or complexes. As another example,the substrate can be a microtiter or similar plate having wells so thateach composition or complex is in a region separated from othercompounds in other regions by a physical barrier. The array may alsocomprise a parallel reactor or testing chamber.

[0188] The array typically comprises at least 8 compounds, complexes orcompositions each having a different chemical formula, meaning thatthere must be at least one different atom or bond differentiating themembers in the array or different ratios of the components referred toherein (with components referring to ligands, metal precursors,activators, group 13 reagents, solvents, monomers, supports, etc.). Inother embodiments, there are at least 20 compounds, complexes orcompositions on or in the substrate each having a different chemicalformula. In still other embodiments, there are at least 40 or 90 or 124compounds, complexes or compositions on or in the substrate each havinga different chemical formula. Because of the manner of formingcombinatorial arrays, it may be that each compound, complex orcomposition may not be worked-up, purified or isolated, and for example,may contain reaction by-products or impurities or unreacted startingmaterials.

[0189] The catalytic performance of the compounds, complexes orcompositions of this invention can be tested in a combinatorial or highthroughput fashion. Polymerizations can also be performed in acombinatorial fashion, see, e.g., U.S. Patent Application No.09/239,223, filed Jan. 29, 1999; U.S. Patent No. 6,306,658 and WO00/09255, each of which is herein incorporated by reference.

EXAMPLES

[0190] General: All reactions were performed under a purified argon ornitrogen atmosphere in a Vacuum Atmospheres glove box. All solvents usedwere anhydrous, de-oxygenated and purified according to knowntechniques. All ligands and metal precursors were prepared according toprocedures known to those of skill in the art, e.g., under inertathmosphere conditions, etc. Ethylene/styrene and ethylene/1-octenecopolymerizations and propylene polymerizations were carried out in aparallel pressure reactor, which is fully described in pending U.S.patent applications Nos. 09/177,170, filed Oct. 22, 1998, 09/239,223,filed Jan. 29, 1999, and WO 00/09255, and U.S. Pat. No. 6,306,658 eachof which is incorporated herein by reference.

[0191] High temperature Size Exclusion Chromatography was performedusing an automated “Rapid GPC” system as described in U.S. Pat. Nos.6,175,409, 6,260,407, and 6,294,388 each of which is incorporated hereinby reference. In the current apparatus, a series of two 30 cm×7.5 mmlinear columns, with one column containing PLgel 10 um, MixB and theother column containing PLgel 5 um, MixC (available from Polymer Labs).The GPC system was calibrated using narrow polystyrene standards. Thesystem was operated at a eluent flow rate of 1.5 mL/min and an oventemperature of 160° C. o-dichlorobenzene was used as the eluent. Thepolymer samples were dissolved 1,2,4-trichlorobenzene at a concentrationof about 1 mg/mL. Between 40 μL and 200 μL of a polymer solution wereinjected into the system. The concentration of the polymer in the eluentwas monitored using an evaporative light scattering detector. All of themolecular weight results obtained are relative to linear polystyrenestandards.

[0192] The ratio of 1-octene to ethylene incorporated in theethylene-octene copolymer products was determined by FTIR. FTIR wasperformed on a Bruker Equinox 55+IR Scope II in reflection mode using aPike MappIR accessory with 16 scans. The ratio of 1-octene to ethyleneincorporation was represented as the weight % (wt. %) of 1-octeneincorporated in the polymer (wt. % 1-octene). Wt.% 1-octene was obtainedfrom ratio of band heights at 1378 cm⁻¹ and 4335cm⁻¹. This method wascalibrated using a set of ethylene/1-octene copolymers with a range ofknown wt. % 1-octene content.

[0193] Crystallinity in polypropylene was determined by FTIRspectroscopy. FTIR spectra of thin films deposited from solution ontogold coated Si wafers are acquired at 4 cm⁻¹ resolution and with 16scans in reflection-absorption mode on a Bruker Equinox 55 FTIRspectrometer equipped with a Pike MappIR accessory. The height ratio oftwo bands at 995 cm⁻¹ (C—H bending and CH₃ rocking mode from regularcrystalline isotactic helices) and 972 cm⁻¹ (coupled C—C stretching andCH₃ rocking mode, independent of crystallinity) is determined as ameasure of isotacticity (as known in the art, see, e.g., J. P. Luongo,J. Appl. Polym. Sci 3 (1960) 302-309, and T. Sundell, H. Fagerholm, H.Crozier, Polymer 37 (1996) 3227-323 1, each of which is incorporatedherein by reference). For blends of atactic and isotactic polypropylene(PP) with 0-70% isotactic PP, the IR ratio is proportional to thepercentage of isotactic PP. For greater than 98% isotactic PP the ratiois greater than 0.95, for amorphous PP the ratio is 0.2.

[0194] The ratio of styrene to ethylene incorporated in the polymerproducts, represented as the mol % of styrene incorporated in thepolymer (mol % styrene) was determined using FTIR spectroscopy. The IRspectra (16 scans at 4 cm⁻¹ resolution) analyzed by Partial LeastSquares (PLS) analysis with PLSplus/IQ V3.04 for GRAMS/32 (GalacticIndustries) software, using the following training set for calibration.

[0195] Training set

[0196] The analysis based on a training set consisting of 180 spectra ofblends of ethylene-styrene copolymers with known styrene incorporation,and atactic homo-polystyrene. The 16 known copolymers had between 1 and47 mol % incorporated styrene. The atactic homo-polystyrene content inthe blends ranged from 0 to 90% of the total styrene content of theblend. Most blends are prepared from copolymers with up to 20 mol %incorporation. Multiple spectra per blend were included in the trainingset.

[0197] Preprocessing of the Spectra

[0198] Mean centering; linear baseline correction based on averageabsorbances at 2074 cm⁻¹-2218 cm⁻¹ and 3224 cm⁻¹-3465 cm⁻¹; thicknesscorrection based on band area from 1483 cm⁻¹ to 1504 cm⁻¹ with baselinefrom 1389 cm⁻¹-1413 cm⁻¹ to 1518 cm⁻¹-1527 cm⁻¹.

[0199] Analysis

[0200] PLS-1 algorithm; spectral regions 499 cm⁻¹ to 2033 cm⁻¹ and 3577cm⁻¹ to 4495 cm⁻¹. Prediction of number ratios of atactichomo-polystyrene to total styrene (∝ % atactic homo-polystyrene to totalstyrene) with 10 factors and ethylene to total styrene (∝ mol % totalstyrene) with 7 factors and calculation of mol % incorporated styrenefrom these 2 numbers.

[0201] The ratio of styrene to ethylene incorporated in the polymerproducts, represented as the weight % (wt. %) of styrene incorporated inthe polymer (wt. % styrene) can also be determined using ¹H NMRspectroscopy.

[0202] Differential Scanning Calorimetry (DSC) measurements wereperformed on a TA instrument DSC 2920 to determine the melting point ofpolymers. The sample was equilibrated at 200° and held for 4 minutes.The sample was cooled with a rate of 10° C. per minute to 55° C. whereit was held for 10 minutes. The sample was cooled further to −50° C.with a rate of 10° C./min and held at −50° C. for 4 minutes. Then, thesample was heated to 200° C. at a rate of 1° C./min and data werecollected during that heating period.

[0203] Ethylene/isobutylene copolymerizations were carried out in aparallel pressure reactor equipped with a magnetic stirrer hotplate. Theratio of isobutylene to ethylene incorporated in the polymer products,represented as the weight % (wt. %) of isobutylene incorporated in thepolymer (wt. % IB) was determined using ¹H NMR spectroscopy.

[0204] The following ligands are used in some of these examples:

[0205] These ligands were prepared using techniques known to those ofskill in the art, for example, using the following general experimental:

[0206] Part A: Synthesis of 2-bromo-6-formylpyridine

[0207] To a solution of 23.7 g (100 mmol) of 2,6-dibromopyridine in 150mL of anhydrous, degassed THF cooled to −78° C. was added dropwise underN₂ a solution of 11.0 mL (110 mmol) of 10.0 M ^(n)BuLi in 150 mL ofanhydrous, degassed Et₂O. After 2 h at −78° C., 24.2 mL (300 mmol) ofanhydrous, degassed DMF was added dropwise with rapid stirring. Thissolution was stirred at −78° C. for 2 h, then allowed to warm to RTovernight.

[0208] The solution was cooled to −78° C. and 100 mL of 1.0 M aq. HClwas added slowly. The organic phase was separated and the aqueous phasewas washed with 3×50 mL Et₂O. The organic washes were combined andwashed with 3×50 mL H₂O and 3×50 mL brine, then dried over Na₂SO₄. Thevolatiles were removed in vacuo to provide an orange oil. The oil wastriturated with hexanes to give a pale orange solid that was washed withcold pentane and dried under vacuum overnight.

[0209] Part B: Synthesis of 2-formyl-6-naphthylpyridine

[0210] Naphthylboronic acid (2.06 g, 12 mmol) and Na₂CO₃ (2.65 g, 25mmol) were dissolved in 60 mL of degassed 4:1 H₂O/MeOH. This solutionwas added via cannula to a solution of 1.86 g (10 mmol) of2-bromo-6-formylpyridine and 116 mg (0.10 mmol) of Pd(PPh₃)₄ in 50 mL ofdegassed toluene. The biphasic solution was vigorously stirred andheated to 70° C. under N₂ for 4 h. On cooling to RT, the organic phasewas separated and washed with 3×25 mL of Et₂O. The combined organicextracts were washed with 3×25 mL of H₂O and ×20 mL of brine and driedover Na₂SO₄. After removing the volatiles in vacuo, the resultant brownoil was chromatographed on silica with 0-50% hexanes/CH₂Cl₂. The earlyfractions contained naphthalene and binaphthyl and were discarded. Theremaining fractions were combined and the volatiles were removed toprovide 2-formyl-6-naphthlypyridine as a white solid.

[0211] Part C: Synthesis of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine

[0212] A solution of 1.17 g (0.5 mmol) of 2-formyl-6-naphtlypyridine and0.98 g (0.55 mmol) of 2,6-diisopropylaniline in 50 mL of anhydrous THFcontaining 3 Å sieves and a catalytic amount of TsOH was heated toreflux under N₂ for 12 h. After filtration and removal of the volitilesin vacuo, the crude material was passed through a 4×6 cm plug of neutralalumina with 1: 1 hexanes/ CH₂Cl₂ eluent. Removal of the volitilesprovided 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine as yellowcrystals.

[0213] Part D: Synthesis of(6-naphthyl-2-pyridyl)-N-(2,6-diisopropylphenyl)benzylamine (Ligand L4)

[0214] Synthesis With MgBr₂ Precomplexation:

[0215] To a well-stirred slurry of powdered MgBr₂ (184 mg, 1 mmol) in 2mL of anhydrous, degassed Et₂O was added under N₂ a solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (392 mg, 1 mmol) in 2mL of Et₂O. The mixture was sonicated until the yellow color of theimine dissipated and a free-flowing pale yellow powder was formed. Tothis suspension was added with vigorous stirring a solution ofphenyllithium (833 uL of 1.8 M in cyclohexane, 1.5 mmol). After stirringat RT for 12 h, the reaction was quenched with aq. NH₄Cl. The organiclayer was separated, washed with brine and H₂O, then dried over Na₂SO₄.Following chromatography (silica gel, 3% THF/hexanes), the product wasisolated as a colorless oil.

[0216] Synthesis Without MgBr₂ Precomplexation:

[0217] To a solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (392 mg, 1 mmol) in 5mL of anhydrous, degassed Et₂O cooled to −30° C. under N₂ was added asolution of phenyllithium (833 uL of 1.8 M in cyclohexane, 1.5 mmol).After warming to RT over 1 h. the soln. was stirred at RT for 12 h. Thereaction was then quenched with aq. NH₄Cl, and worked-up as above.

[0218] This same procedure is followed for the different ligands, butwith the following different starting materials for the differentligands:

[0219] In part B:

[0220] In Part C:

[0221] In part D:

[0222] For ligand L28, the last step in the reaction sequence (part D)is a reduction reaction using sodiumtriacetozyborohydride (Na(Oac)₃BH)in THF for 1-3 days following aq. NH₄Cl quench and work-up as it isdescribed in Part D above.

Example 1 Synthesis of Ligand

[0223]

[0224] Both parts to this example make the same ligand, shown above,with and without the presence of complexing agent.

[0225] Part A: Synthesis without MgBr₂ Complexation:

[0226] To a solution of 2-pyridyl-N-mesitylimine (224 mg, 1 mmol) in 5mL of anhydrous, degassed Et₂O cooled to −30° C. was added under argon asolution of phenyllithium (833 μL of 1.8 M in cyclohexane, 1.5 mmol).After warming to room temperature over 1 hour, the solution was stirredfor a further 12 hours. The reaction was then quenched with aqueousNH₄Cl, the layers were separated, and the organic layer was dried overNa₂SO₄. GC-MS analysis showed a mixture of the C- and N-alkylatedproducts. The C- to N-alkylation ratio was 4:1 as determined by ¹H NMR.

[0227] Part B: Synthesis with MgBr₂ Complexation:

[0228] To a stirred slurry of powdered MgBr₂ (92 mg, 0.5 mmol) in 1 mLof anhydrous, degassed Et₂O was added under argon a solution of2-pyridyl-N-mesitylimine (224 mg, 1 mmol) in 5 mL of Et₂O. The mixturewas stirred for 2 hours until the yellow color of the imine dissipatedand a pale yellow solid was formed. After cooling to −30° C., a solutionof phenyllithium (833 μL of 1.8 M in cyclohexane, 1.5 mmol) was addedwith stirring. After warming to room temperature over 1 hour, thesolution was stirred for a further 12 hours. The reaction was worked upas above. GC-MS analysis showed exclusive formation of the C-alkylatedproduct. Following chromatography (silica, 10% ethyl acetate/hexanes),the product was isolated as a colorless solid (266 mg, 88%).

Examples 2-3

[0229] Preparation of the polymerization reactor prior to injection ofcatalyst composition; Ethylene-1-octene Polymerizations: A pre-weighedglass vial insert and disposable stirring paddle were fitted to eachreaction vessel of the reactor. The reactor was then closed, 0. 100 mLof a 0.02 M solution of triisobutylaluminium (TIBA) in toluene, then2.375 mL of toluene, then 0.250 mL of 1-octene, then 2.375 mL oftoluene, were injected into each pressure reaction vessel through avalve. The temperature was then set to 130° C., and the toluene/l-octenemixture was exposed to ethylene gas at 100 psi pressure. An ethylenepressure of 100 psi in the pressure cell and the temperature settingwere maintained, using computer control, until the end of thepolymerization experiment.

[0230] Preparation of the polymerization reactor prior to injection ofcatalyst composition; Ethylene-Styrene Polymerizations: A pre-weighedglass vial insert and disposable stirring paddle were fitted to eachreaction vessel of the reactor. The reactor was then closed, 0.100 mL ofa 0.02 M solution of triisobutylaluminium (TIBA) in toluene, then 4.50mL of toluene, were injected into each pressure reaction vessel througha valve. The temperature was then set to 110° C., and the toluenemixture was exposed to ethylene gas at 100 psi pressure. An ethylenepressure of 100 psi in the pressure cell and the temperature settingwere maintained, using computer control, until the end of thepolymerization experiment.

[0231] Ethylene-1-octene and Ethylene-Styrene Polymerizations: Thepolymerization reactions were allowed to continue for 30 minutes, duringwhich time the temperature and pressure were maintained at their pre-setlevels by computer control. After 30 minutes, the ethylene flow to thereactor vessel was stopped. The temperature was then allowed to drop tobelow 80° C. and the ethylene pressure in the cell was vented.

[0232] Product work up: Ethylene-1-octene Polymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the ratio of 1-octene to ethylene incorporated in thepolymer product, represented as the weight % of 1-octene incorporated inthe polymer.

[0233] Product work up: Ethylene-Styrene Polymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by ¹H NMR spectroscopyto determine the ratio of styrene to ethylene incorporated in thepolymer product, represented as the weight % of styrene incorporated inthe copolymer.

[0234] Presentation of results: Tables 3-5 present results fromlibraries of polymerizations, using the following key (Tables 3 and 4are in FIGS. 3 and 4, respectively):

Example 2 Ethylene-1-octene Polymerizations using Hafnium-LigandCompositions

[0235] Preparation of Stock Solutions: The “group 13 reagent solution”is a 0.20 M solution of triisobutylaluminium (TIBA). The “activatorsolution” is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0236] In situ preparation of Hafnium-ligand compositions: Stocksolutions were prepared as follows: The “metal precursor solution” is a25 mM solution of Hf(CH₂C₆H₅)₄ in toluene (34 mg in 2.50 mL toluene;HfCl₄ was purchased from Strem Chemicals, Inc., Newburyport, Mass.(99.95%+Hf) and modified with 4 equivalents of benzyl Gringard at −30°C. in ether). The “ligand solutions” are a 25 mM solution the respectiveligands in toluene, prepared in an array of 1 mL glass vials by adding0.060 mL of toluene to 1.5 μmol of the ligand in a 1 mL glass vial. Toeach 1 mL glass vial containing ligand/toluene solution was added 0.060mL of the metal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions we allowed to sit at room temperaturefor 1 hour prior to addition of TIBA solution and injection into thereactor, as described below. Table 3 illustrates the hafnium-ligandsolutions prepared in this example.

[0237] Injection of solutions into the pressure reactor vessel: Afterthe toluene/1-octene mixture was saturated with ethylene at 100 psipressure, 0.075 mL (15 μmol) of the group 13 reagent solution was addedto the 1 mL vial. About 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL 25 of toluene,were injected into the reaction vessel. About another 30 seconds later,0.170 mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 3, which is presented in FIG. 3.

Comparative Example Ethylene-1-octene Polymerizations usingZirconium-Ligand Compositions

[0238] Preparation of Stock Solutions: The “group 13 reagent solution”is a 0.20 M solution of triisobutylaluminium (TIBA). The “activatorsolution” is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0239] In situ preparation of Zirconium-ligand compositions: Stocksolutions were prepared as follows: The “metal precursor solution” is a25 mM solution of Zr(CH₂C₆H₅)₄ in toluene (28.5 mg in 2.50 mL toluene).The “ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions were allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 4 illustrates thezirconium-ligand solutions prepared in this comparative example.

[0240] Injection of solutions into the pressure reactor vessel: Afterthe toluene/1-octene mixture was saturated with ethylene at 100 psipressure, 0.075 mL (15 μmol ) of the group 13 reagent solution was addedto the 1 mL vial. About 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL of toluene, wereinjected into the reaction vessel. About another 30 seconds later, 0.170mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 4, which is presented in FIG. 4.

Example 3 Ethylene-Styrene Polymerizations using Hafnium-LigandCompositions

[0241] Preparation of Stock Solutions: The “group 13 reagent solution”is a 0.20 M solution of triisobutylaluminium (TIBA). The “activatorsolution” is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0242] In situ preparation of Hafnium-ligand compositions: Stocksolutions were prepared as follows: The “metal precursor solution” is a25 mM solution of Hf(CH₂C₆H₅)₄ in toluene (34 mg in 2.50 mL toluene;HfCl₄ was purchased from Strem Chemicals, Inc., Newburyport, Mass.(99.95%+Hf) and modified with 4 equivalents of benzyl Gringard at −30°C. in ether). The “ligand solutions” are a 25 mM solution the respectiveligands in toluene, prepared in an array of 1 mL glass vials by adding0.060 mL of toluene to 1.5 μmol of the ligand in a 1 mL glass vial. Toeach 1 mL glass vial containing ligand/toluene solution was added 0.060mL of the metal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions were allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 5 illustrates thehafnium-ligand solutions prepared.

[0243] Injection of solutions into the pressure reactor vessel: Afterthe toluene mixture was saturated with ethylene at 100 psi pressure,0.500 mL of styrene followed immediately by 0.500 mL of toluene, wereinjected into the pressure reaction vessel. About 30 seconds later,0.075 mL (15 μmol) of the group 13 reagent solution was added to the 1mL vial. About another 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL of toluene, wereinjected into the reaction vessel. About another 30 seconds later, 0.170mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 5.

Comparative Example Ethylene-Styrene Polymerizations usingZirconium-Ligand Compositions

[0244] Preparation of Stock Solutions: The “group 13 reagent solution”is a 0.20 M solution of triisobutylaluminium (TIBA). The “activatorsolution” is a 10 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (160 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0245] In situ preparation of zirconium-ligand compositions: Stocksolutions were prepared as follows: The “metal precursor solution” is a25 mM solution of Zr(CH₂C₆H₅)₄ in toluene (28.5 mg in 2.50 mL toluene).The “ligand solutions” are a 25 mM solution the respective ligands intoluene, prepared in an array of 1 mL glass vials by adding 0.060 mL oftoluene to 1.5 μmol of the ligand in a 1 mL glass vial. To each 1 mLglass vial containing ligand/toluene solution was added 0.060 mL of themetal precursor solution (1.5 μmol), to form the metal-ligandcombination solution. To each metal-ligand combination solution was thenadded 0.060 mL of a 0.5 M 1-octene solution in toluene (30 μmol of1-octene). The resultant solutions was allowed to sit at roomtemperature for 1 hour prior to addition of TIBA solution and injectioninto the reactor, as described below. Table 5 illustrates thezirconium-ligand solutions prepared:

[0246] Injection of solutions into the pressure reactor vessel: Afterthe toluene mixture was saturated with ethylene at 100 psi pressure,0.500 mL of styrene followed immediately by 0.500 mL of toluene, wereinjected into the pressure reaction vessel. About 30 seconds later,0.075 mL (15 μmol) of the group 13 reagent solution was added to the 1mL vial. About another 30 seconds later, 0.100 mL (1.0 μmol) of the“activator solution” followed immediately by 0.400 mL of toluene, wereinjected into the reaction vessel. About another 30 seconds later, 0.170mL of the 1 mL vial contents, followed immediately by 0.330 mL oftoluene, were injected into the reaction vessel. Results are presentedin Table 5. TABLE 5 Hf(CH₂C₆H₅)₄ and Zr(CH₂C₆H₅)₄-Ligand Compositions:Ethylene- Styrene Copolymerization Results: Zr(CH₂C₆H₅)₄ Hf(CH₂C₆H₅)₄Yield wt. % Styrene Yield wt. % Styrene Ligand (mg) by NMR (mg) by NMR

152 6 469 14

209 7 326 15

138 7 295 15

163 7 278 10

134 6 153 15

Example 3A Ethylene-Styrene Polymerizations using Hafnium-LigandCompositions

[0247] This example comprises four polymerization reactions carried outwith different ligand/hafnium compositions for the copolymerization ofethylene and styrene. The results are summarized in Table 5A, along withfour comparative examples of polymerization reactions carried out withdifferent ligand/zirconium compositions for the copolymerization ofethylene and styrene.

[0248] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.10 mL of a 0.02 M solution ofdiisobutylaluminiumhydride (“DIBAL”) in toluene and 3.8 mL of toluenewere injected into each pressure reaction vessel through a valve. Thetemperature was then set to 110° C., and the stirring speed was set to800 rpm, and the mixture was exposed to ethylene at 100 psi pressure. Anethylene pressure of 100 psi in the pressure cell and the temperaturesetting were maintained, using computer control, until the end of thepolymerization experiment.

[0249] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) in toluene.

[0250] In situ preparation of metal-ligand compositions: Stock solutionswere prepared as follows: The “metal precursor solution” is a 10 mMsolution of Hf(NMe₂)₄ in toluene. The “ligand solutions” are 25 mMsolutions of the representative ligands in toluene, prepared in an arrayof 1 mL glass vials by dispensing 0.030 mL of a 25 mM ligand solution ina 1 mL glass vial. To each 1 mL glass vial containing ligand/toluenesolution was added 0.075 mL of the metal precursor solution (0.75 μmol),to form the metal-ligand combination solution. The reaction mixtures weallowed to sit at 80° C. for 2-3 hours during which time most of thesolvent evaporates. The reaction mixtures were dried completely byblowing a stream of Argon over the 1 mL vial. Prior to addition ofalkylation and activator solution, a small amount of solvent (0.020 mL)was added to the dry composition.

[0251] Activation and Injection of solutions into the pressure reactorvessel: To the ligand metal composition, 0.037 mL of a 500 mM solutionof 1-octene in toluene and 0.020 mL of toluene and 0.112 mL of the group13 reagent solution was added to the 1 mL vial. Around 11 min later,0.420 mL of styrene followed immediately by 0.380 mL of toluene, wereinjected into the prepressurized reaction vessel. Another 1 min later,0.165 mL (0.845 μmol) of the “activator solution” was added to the 1 mLvial. About another 30 seconds later, 0.181 mL of the 1 mL vialcontents, followed immediately by 0.619 mL of toluene, were injectedinto the reaction vessel.

[0252] Polymerization: The polymerization reaction was allowed tocontinue for the 217-601 seconds, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction. Thespecific times for each polymerization are shown in table 5B the columntitled Hf(NMe₂)₄. After the reaction time elapsed, the reaction wasquenched by addition of an overpressure of carbon dioxide.

[0253] Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in Table5A in the column titled Hf(NMe₂)₄.

Comparative Example Ethylene-Styrene Polymerizations usingZirconium-Ligand Compositions:

[0254] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of the experiment was performed asdescribed above for Example 3A using Hafnium-ligand compositions.

[0255] Preparation of the group 13 reagent and activator stocksolutions: This part of the experiment was performed as described abovefor Example 3A using Hafnium-ligand compositions.

[0256] In situ preparation of metal-ligand compositions: This part ofthe experiment was performed as described above for Example 3A usingHafnium-ligand compositions except that the “metal precursor solution”is a 10 mM solution of Zr(NMe₂)₄ in toluene.

[0257] Activation and Injection of solutions into the pressure reactorvessel: : This part of the experiment was performed as described abovefor Example 3A using Hafnium-ligand compositions.

[0258] Polymerization: This part of the experiment was performed asdescribed above for Example 3A using Hafnium-ligand compositions, exceptthat the polymerization reaction was allowed to continue for the 399-600seconds. The specific times for each polymerization are shown in table5B in the column titled Zr(NMe₂)₄.

[0259] Product work up: ethylene/styrene copolymerizations: This part ofthe experiment was performed as described above for Example 3A usingHafnium-ligand compositions. Results are presented in Table 5A in thecolumn titled Zr(NMe₂)₄. TABLE 5A Hf(NMe₂)₄ and Zr(NMe₂)₄-LigandCompositions: Ethylene-Styrene Copolymerization Results (Example 3A):Hf(NMe₂)₄ Zr(NMe₂)₄ mol % mol % styrene styrene Ligand Activity (FTIR)Activity (FTIR) L29 57 2.8 23 0.8 L30 158 3.0 77 2.0 L4 111 3.1 35 1.6L5 57 3.3 41 1.9

[0260] In Table 5A, Activity is shown in units of mg polymer per minuteper μmol of Hf or Zr, mol % styrene is as determined by FTIR using PLSanalysis, as described above. TABLE 5B Polymerization times in secondsfor example 3A Hf(NMe₂)₄ Zr(NMe₂)₄ Polymerization Polymerization Ligandtime time L29 601 600 L30 217 399 L4 293 600 L5 601 601

Example 4 Ethylene-Isobutylene Copolymerizations using Hafnium-LigandCompositions

[0261] Preparation of Stock Solutions: The “group 13 reagent solution”is a 20 mM solution of triethylaluminum (TEAL). The “activator solution”is a 5 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene (75 mg in 20 mL toluene),heated to approximately 85° C. to fully dissolve theN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate. The “metalprecursor solution” is a 20 mM solution of Hf(CH₂C₆H₅)₄ in toluene (33mg in 2.0 mL toluene). The “ligand solutions” are 20 mM solutions of theligand shown below in Table 6 in toluene.

[0262] Ethylene-Isobutylene Copolymerizations: Pre-weighed glass vialseach containing a disposable magnetic stir bar were placed into thepositions of the reactor block. Using a liquid dispensing robot, 2.9 mLof toluene are added to these glass vials, followed by 0.180 mL of“ligand solution” and 0.200 mL of Hf(CH₂C₆H₅)₄ in toluene. Thesesolutions were stirred for 30 minutes at room temperature after which0.02 mL of a 20 mM solution of triethylaluminum (TEAL) in toluene weredispensed into each reaction vessel. Following a 10 minute waitingperiod, 0.700 mL of a 5 mM solution of N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene were added to each vial.The reactor was then closed, exposed to an ethylene/isobutylene gasmixture (ethylene feed 5 psi/isobutylene feed 10 psi pressure) andplaced on a stirrer hotplate maintained at 50° C. for the duration ofthe experiment. After 60 minutes, the reactor was removed from thestirrer hotplate. The gases were vented from the reactor, the reactoropened and the glass vials removed.

[0263] Product work up: Ethylene-Isobutylene Polymerizations: The glassvials, containing the polymer product and solvent, were removed from thereactor and removed from the inert atmosphere dry box, and the volatilecomponents were allowed to evaporate at room temperature in the air.After most of the volatile components had evaporated, the vial contentswere dried thoroughly by evaporation under vacuo. The vial was thenweighed to determine the yield of polymer product. The polymer productwas then analyzed by ¹H NMR spectroscopy to determine the ratio ofisobutylene to ethylene incorporated in the polymer product, representedas the weight % of isobutylene incorporated in the copolymer. Table 6shows a summary of the results: TABLE 6 Hf(CH₂C₆H₅)₄-LigandCompositions: Ethylene-Isobutylene Copolymerization Results: LigandYield (mg) Wt. % IB

97 33

Examples 5-10 Synthesis of Ligand/Metal Complexes 1-21.

[0264]

Example 5 Synthesis of Complex 1 (C 1)

[0265] The ligand L4 used in this example was prepared in the mannerdescribed above.

[0266] Hf(NMe₂)₄ (291 mg, 0.82 mmol) and L4, from above, (358 mg, 0.76mmol) were combined in 5 mL C₆D₆. The reaction was heated to 70° C. andvented occasionally. Aliquots were analyzed by ¹H NMR every hour untilthe reaction was complete (3 hours). Solvent was then removed, yieldinga yellow glassy solid, which was extracted with hot pentane (20 mL) andfiltered. The volume of the filtrate was reduced to 5 mL and then cooledto −35° C. A yellow microcrystalline powder was collected (439 mg, 74%)¹H NMR (δ C₆D₆). 6.55-7.75 (overlapping m, 17H total, Ar), 5.93, (s, 1H,CHpy), 3.65 (sept, 1H, CH-iPr), 3.31 (sept, 1H, CH-iPr), 2.83 (br s, 6,NMe₂), 2.67 (br s, 6, NMe₂), 2.22 (br s, 6, NMe₂), 1.64 (d, 3H, CHMe₂),1.53 (d, 3H, CHMe₂), 1.23 (d, 3H, CHMe₂), 0.26 (d, 3H, CHMe₂). Crystalssuitable for X-ray analysis were obtained by re-crystallization from hothexane and submitted for single crystal X-ray analysis, which confirmedthe structure shown above.

Example 6 Synthesis of complex 2 (C 2)

[0267] The ligand L5 used in the example was prepared in the mannerdescribed above.

[0268] Hf(NMe₂)₄ (121 mg, 0.34 mmol) and L5, from above, (130 mg, 0.31mmol) were combined in 5 mL toluene. The reaction was heated to 110° C.and vented occasionally. Aliquots were analyzed by ¹H NMR until thereaction was complete (24 hours). Solvent was then removed, yielding ayellow glassy solid, which was extracted with hot pentane (20 mL) andfiltered. The volume of the filtrate was reduced to 5 mL and then cooledto −35° C. A yellow microcrystalline powder was collected (150 mg; 71%).¹H NMR (δ C₆D₆). 8.36, 7.69 (d, 1H each, Ar) 6.9-7.5 (overlapping m, 12Htotal, Ar), 6.55 (d, 1H, Ar) 6.10, (s, 1H, CHpy), 3.50 (sept, 1H,CH-iPr), 3.18 (s, 6 NMe₂), 2.88 (s, 6, NMe₂), 1.52 (d, 3H, CHMe₂), 1.39(d, 3H, CHMe₂), 1.17 (d, 3H, CHMe₂), 0.49 (d, 3H, CHMe₂). Crystalssuitable for x-ray diffraction were obtained by recrystallization fromhot pentane and submitted for single crystal X-ray analysis, whichconfirmed the structure shown above.

Example 7A and 7B

[0269] 7A Synthesis of complex 3 (C 3): Complex 1, from Example 5 above,(51 mg, 0.065 mmol) was dissolved in 7 mL pentane. The mixture wascooled to −35° C. and a 2.0 M solution of AlMe₃ in toluene (330 μL, 0.66mmol, 10 eq.) was added. A yellow precipitate formed and thenredissolved as the reaction was allowed to warm to room temperature. Themixture was stirred at room temperature for 1 hour, and then the solventwas removed. The resulting yellow powder was recrystallized from pentaneat −35° C. Yellow microcrystals (25 mg) were collected and dried. Asecond crop yielded an additional 7 mg of crystals. (combined yield=73%)¹H NMR (C₆D₆). 8.56, 8.23, 7.80, 7.72, 7.46 (d, 1 H each, Ar) 7.0-7.4(overlapping m, 10H total), 6.40 (d, 1H, Ar), 5.92, (s, 1H, CHpy), 3.82(sept, 1H, CH-iPr), 3.27 (sept, 1H, CH-iPr), 1.38 (overlapping two d, 6Htotal, CHMe₂), 1.15 (d, 3H, CHMe₂), 0.93 (s, 3H, Hf-Me), 0.65 (s, 3H,Hf-Me), 0.38 (d, 3H, CHMe₂).

[0270] 7B Synthesis of complex 11 (C 11): In a manner similar to thatdescribed in example 7A, complex 11 was synthesized from complex 10.

Examples 8A-8F

[0271] 8A: Synthesis of complex 4 (C 4): The ligand used in the examplewas prepared in the manner generally described above for L1, shownabove.

[0272] In a manner similar to that described in example 6, the complexwas prepared from L1, from above, (48 mg, 0.11 mmol) and Hf(NMe₂)₄ (0.12mmol) in C₆D₆. The mixture was heated to 100° C. for 24 hours, and thenrecrystalized from pentane (44 mg, 58%). ¹H NMR was consistent with theformation of the complex whose structure is shown above.

[0273] 8B: Synthesis of complex 6 (C6): The ligand used in the examplewas prepared in the manner generally described above for L5, shownabove.

[0274] In a manner similar to that described in example 7, complex 6whose structure is shown above was prepared from L5, from above, (20 mg,0.05 mmol) and Zr(NMe₂)₄ (13 mg, 0.05 mmol) in C₆D₆. After heating to100° C. for 24 hours, yellow crystals were obtained by recrystallizationfrom pentane. (yield=15 mg, 50%). ¹H NMR was consistent with theformation of the complex.

[0275] 8C: Synthesis of complex 12 (C 12): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L20, from above.

[0276] 8D: Synthesis of complex 13 (C 13): In a manner similar to thatdescribed in example 7, complex 13 whose structure is shown above wasprepared from L2 1, from above.

[0277] 8E: Synthesis of complex 15 (C 15): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L23, from above.

[0278] 8F: Synthesis of complex 16 (C 16): In a manner similar to thatdescribed in example 7, complex 12 whose structure is shown above wasprepared from L24, from above.

Examples 9A -9F

[0279] 9A Synthesis of complex 5: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L3, from above, (43 mg, 0.09mmol) and Hf(NMe₂)₄ (56 mg, 0.16 mmol) in C₆D₆. The mixture was heatedto 100° C. for 48 hours, and then recrystalized from pentane (46 mg,66%). ¹H NMR was consistent with the formation of the complex.

[0280] 9B Synthesis of complex 7: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L7, from above.

[0281] 9C Synthesis of complex 8: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L6, from above.

[0282] 9D Synthesis of complex 9: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L9, from above.

[0283] 9E Synthesis of complex 10: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L8, from above.

[0284] 9F Synthesis of complex 14: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L22, from above.

[0285] 9G Synthesis of complex 21: The ligand used in the example wasprepared in the manner generally described above for L4, shown above. Ina manner similar to that described in example 5, the complex whosestructure is shown above was prepared from L30, from above.

Examples 10A-10D Synthesis of Hafnium benzyl complexes C17-C20

[0286] 10A Synthesis of complex 17 (C 17): The ligand used in theexample was prepared in a manner generally described above for L4, shownabove. Ligand L25 (202 mg, 0.53 mmol) was dissolved in 4 mL toluene andsolid Hf(Bz)₄ (306 mg, 0.56 mmol) was added. The solution was stirredfor 1 hour. ¹H NMR of an aliquot of the reaction mixture revealed thatthe reaction was complete. The volume was reduced to 1 mL, and pentane(10 mL) was added. A yellow precipitate was collected, washed withpentane and dried. ¹H NMR was consistent with the proposed formula

[0287] 10B Synthesis of complex 18 (C 18): The ligand used in theexample was prepared in a manner generally described above for L4, shownabove. In a manner similar to that descibed in example 10A, the complexwhose structure is shown above was prepared from L26 and Hf(CH₂Ph)₄ inC₆D₆.

[0288] 10C Synthesis of complex 19 (C 19): The ligand used in theexample was prepared in a manner generally described above for L4, shownabove. In a manner similar to that descibed in example 10A, the complexwhose structure is shown above was prepared from L27 and Hf(CH₂Ph)₄ inC₆D₆.

[0289] 10D Synthesis of complex 20 (C 20): The ligand used in theexample was prepared in a manner generally described above for L4, shownabove. In a manner similar to that descibed in example 10A, the complexwhose structure is shown above was prepared from L28 and Hf(CH₂Ph)₄ inC₆D₆.

Examples 11-14, 16-24 Presentation of the results

[0290] In the following Examples 11-14 and 16-24, the polymerizationscarried out for the particular example are represented in the firsttable within each example. This first table within each exampledescribes the identity of either ligand (L#) or metal complex (C#) usedin each experiment represented as entry in the grid framed by the rowsand columns labeled with letters and numbers respectively. Additionalexperimental details described in the paragraphs :“Preparation of thepolymerization reactor prior to injection of catalyst composition” and“Activation and Injection of solutions into the pressure reactor vessel”such as “group 13 reagent”, t₁, t₂, Injection fraction, Polym. Temp.(abbreviation for polymerization temperature), Premix Temperature andActivator are given in the first table. Experimental details which applyto each experiment in a row of the grid are listed to the right of therow to which they refer. Experimental details which apply to eachexperiment in a column of the grid are listed below the column to whichthey refer.

[0291] For example the experiment 11.B.2. employs complex C1, and forthis example the “group 13 reagent” is TMA, t₁ is 0.5 minutes , t₂ is 10minutes, Injection fraction is 0.066, Polym. Temp. (abbreviation forpolymerization temperature) is 110° C., Premix temperature is 24° C. andActivator is ABF20.

[0292] The data in the subsequent tables of each example are alsorepresented in grid format as entries in grids framed by the rows andcolumns labeled with letters and numbers respectively, such that thedata in each lettered row and numbered column corresponds to theexperiments described in the corresponding lettered and numbered rowsand columns in the first table of each example. For example theexperiment 11.B.2. the reaction time is 217 seconds, the activity is 877mg polymer per minute per μmol, the crystallinity index is 0.83 and theweight average molecular weight is 163,000 (represented in the table as163 k).

Example 11 Propylene Polymerizations at 110° C.

[0293] Sixteen polymerization experiments were carried out in thisexample, using different metal complexes, activator amounts, group 13reagents and activating conditions.

[0294] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.10 mL of a 0.02 M solution of group 13reagents in toluene and 3.9 mL of toluene were injected into eachpressure reaction vessel through a valve. The temperature was then setto the appropriate setting (with specific temperatures for eachpolymerization being listed in table 7, below), and the stirring speedwas set to 800 rpm, and the mixture was exposed to propylene at 100 psipressure. A propylene pressure of 100 psi in the pressure cell and thetemperature setting were maintained, using computer control, until theend of the polymerization experiment.

[0295] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution is either a 0.2 M solutionof diisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftriethylboron (“BEt3”) or a 0.2 M solution of trimethylaluminium (“TMA”)or a solution that is 0.133 M in triethyl boron and 0.066M in diisobutylaluminium hydride (“DIBAL/BEt3”), all “group 13 reagent” solutions weresolutions in toluene.

[0296] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.2 M group 13 reagentsolution was dispensed into a 1 mL vial that was kept at a constantpremix temperature as specified in the table 7. 0.100 mL (0.5 μmol) ofthe metal complex solution (5 mM in toluene) was added to the 1 mL vial.This mixture was held at a premix temperature for a time period of t₁ asindicated in table 7. Then, 0.110 mL (0.55 μmol) of the “activatorsolution” was added to the 1 mL vial. After the time period t₂ elapsed(time listed in table 7), a fraction of the total 1 mL vial contents(listed in table 7), followed immediately by approximately 0.3 mL oftoluene, were injected into the reaction vessel. The array ofexperiments with values for equivalents of group 13 reagent, t₁, t₂ andinjection fraction is described in table 7.

[0297] Polymerization: The polymerization reaction was allowed tocontinue for times shown in table 7A, during which time the temperatureand pressure were maintained at their pre-set levels by computercontrol. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide sent to the reactor. Thepolymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.

[0298] Product work up: Propylene Polymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the crystallinity index. Results are presented in thetables 8-10. TABLE 7 Description of array of polymerization experiments(examples 11.A.1.-11.D.4.) group 13 group 13 1 2 3 4 reagent^(a))reagent^(b)) A C1 C1 C1 C1 10 DIBALI/ BEt3 20 BEt3 B C1 C1 C1 C1 10 TMATMA C C3 C3 C3 C3 10 DIBAL/ BEt3 20 BEt3 D C3 C3 C3 C3 10 TMA TMA t₁(min) 10 0.5 10 0.5 t₂ (min) 0.5 10 0.5 0.5 Injection fraction 0.0660.066 0.066 0.066 Polym. Temp (° C.) 110 110 110 110 Premix Temp (° C.)24 24 52 52 Activator ABF20 ABF20 ABF20 ABF20

[0299] TABLE 7A reaction times in seconds of experiments 11.A.1.-11.D.4.1 2 3 4 A 490 601 601 600 B 214 217 264 213 C 406 601 555 374 D 208 243264 254

[0300] TABLE 8 Activity (mg polymer per minute per μmol) of examples11.A.1.-11.D.4. 1 2 3 4 A 320 198 253 254 B 864 877 648 780 C 503 319300 457 D 872 722 651 649

[0301] TABLE 9 Crystallinity index of examples 11.A.1.-11.D.4. 1 2 3 4 A0.81 0.77 0.79 0.78 B 0.77 0.83 0.78 0.79 C 0.77 0.77 0.79 0.74 D 0.780.75 0.79 0.79

[0302] TABLE 10 Weight average molecular weight (k) of examples11.A.1.-11.D.4. 1 2 3 4 A 174 187 184 196 B 143 163 162 155 C 174 184178 186 D 155 165 168 167

Example 12 Propylene Polymerization using metal complex 1 at differentpolymerization temperatures.

[0303] In this example, forty-eight polymerization reactions werecarried out. The reactor was prepared as in Example 11, above. Inaddition, the polymerization was run in the same manner and thepolypropylene polymer was worked up in the same manner as in Example 11,above.

[0304] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”) or a toluene solution which is 5 mM in N,N′-dimethylaniliniumtertakis(pentafluorophenyl) borate and 10 mM in tris(pentafluorophenyl)borane (referred to in table 5 as“cocktail”). Both solutions are heatedto approximately 85° C. to dissolve the reagent. The group 13 reagentsolution is either a 0.2 M solution of diisobutylaluminiumhydride(“DIBAL”) or a 0.2 M solution of triethylboron (“BEt3”) or a 0.2 Msolution of triisobutylaluminium (“TIBA”) or a solution which is 0.133 Min triethyl boron and 0.033 M in diisobutyl aluminium hydride(“DIBAL/BEt3”) or a solution which is 0.133 M in triethyl boron and0.066 M in triisobutylaluminium (“TIBA/BEt3”).

[0305] Activation and Injection of solutions into the pressure reactorvessel: An appropriate amount based on the equivalents presented intable 11 of a 0.2 M solution of the group 13 reagent is dispensed into a1 mL vial. 0.100 mL of a 5 mM solution of metal complex 1 is added.After 9 minutes, 0.110 mL solution of the “activator solution” intoluene was added to the 1 mL vial, with the appropriate activatorsolution being identified in table 11. About another 30 seconds later afraction of the total 1 mL vial contents (with the fractional amountbeing identified in table 11, such that e.g., 0.2 refers to 20% byvolume), followed immediately by around 0.300 mL of toluene, wereinjected into the reaction vessel. The array of experiments is describedin table 11. The specific times for each polymerization are shown intable 11a. The results are presented in tables 12-15. TABLE 11Description of polymerization experiments using Complex 1 (examples12.A.1-12.H.6): group 13 Group 13 1 2 3 4 5 6 reagent^(a)) reagent^(b))A C1 C1 C1 C1 C1 C1 30 DIBAL DIBAL B C1 C1 C1 C1 C1 C1 10 DIBAL BEt3 CC1 C1 C1 C1 C1 C1 10 DIBAL/ BEt3 BEt3 D C1 C1 C1 C1 C1 C1 30 TIBA TIBA EC1 C1 C1 C1 C1 C1 10 TIBA BEt3 F C1 C1 C1 C1 C1 C1 10 TIBA/ BEt3 20 BEt3G C1 C1 C1 C1 C1 C1 30 BEt3 BEt3 H C1 C1 C1 C1 C1 C1 60 BEt3 BEt3Injection 0.2 0.2 0.2 0.1 0.2 0.2 Fraction Polym. Temp. (° C.) 75 75 9075 75 110 Activator ABF20 ABF20 ABF20 ABF20 Cocktail Cocktail

[0306] TABLE 11A polymerization times in seconds for examples12.A.1.-12.H.6. 1 2 3 4 5 6 A 679 621 296 860 826 313 B 486 480 889 567520 382 C 385 400 472 378 608 225 D 902 901 612 901 901 901 E 900 900901 901 901 901 F 516 507 773 594 689 900 G 900 900 900 900 607 900 H655 457 900 900 464 900

[0307] TABLE 12 Activity (mg polymer per minute per μmol) of examples12.A.1.-12.H.6. 1 2 3 4 5 6 A 390 365 312 473 255 192 B 381 356 237 389195 150 C 681 605 420 1212 288 285 D 108 102 94 145 23 18 E 74 64 61 3420 47 F 403 378 231 588 157 37 G 62 80 n/d 10 158 4 H 176 396 208 36 2364

[0308] TABLE 13 Crystallinity index of examples 12.A.1.-12.H.6. 1 2 3 45 6 A 0.87 0.85 0.84 0.86 0.85 0.85 B 0.84 0.84 0.81 0.84 0.84 0.82 C0.85 0.77 0.83 0.85 0.84 0.81 D 0.89 0.88 0.82 0.89 0.90 0.81 E 0.860.86 0.82 0.82 0.81 0.74 F 0.85 0.82 0.83 0.84 0.84 0.75 G 0.84 0.83 ndnd 0.80 nd H 0.83 0.78 0.86 0.80 0.81 nd

[0309] TABLE 14 Weight average molecular weight (k) of examples12.A.1.-12.H.6. 1 2 3 4 5 6 A 1348 1356  708 1728 1419 166 B 2748 29341112 3852 4469 283 C 1301 1437  714 2022 2844 214 D 2568 2381 1210 30112085 nd E 3819 4071 2109 3675 3944 331 F 2034 2179 1076 2678 3269 271 G4641 4524 nd nd 4008 nd H 3390 2858 1046 3059 3421 nd

[0310] TABLE 15 Melting points in ° C. of examples 12.A.1., 12.A.3,12.A.6., 12.C.1, 12.C.3. and 12.C.6. 1 2 3 4 5 6 A 143 141 138 B C 140139 137

Example 13 Ethylene/Styrene Copolymerization using metal complexes.

[0311] Twenty-three polymerization reactions were run with differentmetal complexes, temperatures, activators and activating conditions forcopolymerization of ethylene and styrene.

[0312] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.10 mL of a 0.02 M group 13 reagent solutionin toluene and 3.8 mL of toluene were injected into each pressurereaction vessel through a valve (see table 16 for the reagents used).The identity of the group 13 reagent solution is given in table 16. Thetemperature was then set to 110° C., and the stirring speed was set to800 rpm, and the mixture was exposed to 20 ethylene at 100 psi pressure.An ethylene pressure of 100 psi in the pressure cell and the temperaturesetting were maintained, using computer control, until the end of thepolymerization experiment.

[0313] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”), both in toluene.

[0314] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.2 M group 13 reagentsolution was dispensed in a 1 mL vial which was kept at a constantpremix temperature as specified in the table 16. Then 0.100 mL of themetal complex solution (5 mM in toluene) was added. This mixture washeld at a premix temperature for a time t₁, as indicated in table 16,during which time, 0.420 mL of styrene followed immediately by 0.380 mLof toluene, were injected into the prepressurized reaction vessel. Then,0.110 mL (0.55 μmol) of the “activator solution” was added to the 1 mLvial. After the time period t₂ elapsed, a fraction (as indicated intable 16) of the total 1 mL vial contents, followed immediately byapproximately 0.3 mL of toluene were injected into the reaction vessel.The array of experiments is described in table 16.

[0315] Polymerization: The polymerization reaction was allowed tocontinue for the 400-600 seconds, during which time the temperature andpressure were maintained at their pre-set levels by computer control,with the specific times for polymerization listed in table 16A. Thepolymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction.After the reaction time elapsed, the reaction was quenched by additionof an overpressure of carbon dioxide.

[0316] Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in thetables 17-19. TABLE 16 Description of array of polymerizationexperiments examples 13.A.1.-13.H.3. group 13 group 13 1 2 3reagent^(a)) reagent^(b)) A C1 C1 C1 30 DIBAL DIBAL B C1 C1 10 DIBALDIBAL C C1 C1 C1 10 TMA TMA D C3 C3 C3 10 DIBAL DIBAL E C3 C3 C3 10 TMATMA F C2 C2 C2 30 DIBAL DIBAL G C2 C2 C2 10 DIBAL DIBAL H C2 C2 C2 10TMA TMA t₁ (min) 10 10 0.8 t₂ (min) 0.5 0.5 0.5 Injection Fraction 0.20.2 0.2 Premix Temp. (° C.) 24 50 50 Activator ABF20 ABF20 ABF20

[0317] TABLE 16A Polymerization times in seconds for 13.A.1.-13.H.3. 1 23 A 601 602 444 B 601 601 n.d. C 601 600 601 D 602 601 553 E 601 602 600F 601 601 601 G 601 601 601 H 600 601 601

[0318] TABLE 17 Activity (mg polymer per minute per μmol) of examples13.A.1.-13.H.3. 1 2 3 A 218 220 286 B 170 171 n.d. C 132 134 154 D 197193 240 E 145 151 166 F 209 215 217 G 174 176 193 H 144 147 151

[0319] TABLE 18 Styrene incorporation (mol %) of examples13.A.1.-13.H.3. 1 2 3 A 2.4 3.0 3.0 B 3.0 3.8 n.d. C 2.9 3.0 3.0 D 3.93.8 3.7 E 3.2 2.7 2.9 F 3.2 3.0 3.1 G 3.2 3.4 3.4 H 2.9 2.7 2.8

[0320] TABLE 19 Weight average molecular weight (k) of examples13.A.1.-13.H.3. 1 2 3 A 228 241 247 B 386 371 n.d. C 480 484 534 D 275276 361 E 461 521 535 F 303 324 359 G 390 430 504 H 467 535 679

Example 14 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

[0321] Twenty-five polymerization reactions were carried out withdifferent ligand/metal compositions, different temperatures, activatorsand activation conditions for the polymerization of propylene. LigandsL1-L5, whose structures and synthesis are shown above, are used in thisexample.

[0322] In situ preparation of metal-ligand compositions: Stock solutionswere prepared as follows: The “metal precursor solution” is a 10 mMsolution of Hf(NMe₂)₄ in toluene. The “ligand solutions” are 25 mMsolutions of the representative ligands in toluene, prepared in an arrayof 1 mL glass vials by dispensing 0.030 mL of a 25 mM ligand solution ina 1 mL glass vial. To each 1 mL glass vial containing ligand/toluenesolution was added 0.075 mL of the metal precursor solution (0.75 μmol),to form the metal-ligand combination solution. The reaction mixtures weallowed to sit at 80° C. for 2-3 hours during which time most of thesolvent evaporates. The reaction mixtures were then dried completely byblowing a stream of Argon over the 1 mL vial. Prior to addition ofalkylation and activator solution, a small amount of solvent (0.020 mL)was added to the dry composition.

[0323] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0324] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftriethylboron (“BEt3”) or a solution which is 0.133 M in triethyl boronand 0.066 M in diisobutyl aluminium hydride (“DIBAL/BEt3”) or a solutionwhich is 0.133 M in triethyl boron and 0.066 M in triisobutylaluminium(“TIBA/BEt3”).

[0325] Injection of solutions into the pressure reactor vessel: To theligand metal composition, 0.030 mL of a 500 mM solution of 1-octene intoluene then 0.028 mL toluene and 0.112 mL of the group 13 reagentsolution was added to the 1 mL vial. After 9 minutes, 0.165 mL (0.83μmol) of the “activator solution” was added to the 1 mL vial. Aboutanother 30 seconds later, 0.044 mL of the 1 mL vial contents, followedimmediately by 0.356 mL of toluene, were injected into the reactionvessel. The array of experiments is described in detail in table 20.

[0326] Propylene Polymerizations and Product work up: This part of thisexample was performed as described in Example 11, above, with specificpolymerization times shown in table 20A. Results are presented in thetables 21-23. TABLE 20 Description of array of polymerizationexperiments for examples 14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A L1 L1L1 L1 L1 L1 B L2 L2 L2 L2 L2 L2 C L3 L3 L3 L3 L3 L3 D L4 L4 L4 L4 L4 L4E L5 Polym. Temp. (° C.) 75 90 110 75 90 110 30 30  30 10/20 10/20 10/20group 13 reagent^(a)) DIBAL DIBAL DIBAL DIBAL/BEt3 DIBAL/BEt3 DIBAL/BEt3group 13 reagent^(b)) DIBAL DIBAL DIBAL BEt3 BEt3 BEt3 Activator ABF20ABF20 ABF20 ABF20 ABF20 ABF20

[0327] TABLE 20A Polymerization times in seconds of examples14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A 263 138 901 250 160 215 B 578253 901 522 372 901 C 783 233 821 521 341 244 D 363 335 901 341 243 262E 409

[0328] TABLE 21 Activity (mg polymer per minute per μmol) of examples14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A 710 635 41 900 786 256 B 103290 43 101 153 37 C 92 344 67 268 215 227 D 204 181 41 677 339 198 E 652

[0329] TABLE 22 Crystallinity index of examples 14.A.1.-14.D.6. and14.E.1. 1 2 3 4 5 6 A 0.73 0.71 0.72 0.72 0.70 0.73 B 0.71 0.67 0.660.66 0.64 0.66 C 0.76 0.70 0.70 0.70 0.65 0.68 D 0.80 0.77 0.79 0.780.76 0.80 E 0.76

[0330] TABLE 23 Weight average molecular weight (k) of examples14.A.1.-14.D.6. and 14.E.1. 1 2 3 4 5 6 A 554 279 90 878 567 158 B 891438 109 668 582 112 C 1391 497 93 1136 488 95 D 803 489 106 980 661 149E 463

Example 15 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

[0331] Example 15.A. -15.F:

[0332] Six polymerization reactions were carried out with differentligand/metal compositions for the polymerization of propylene.Preparation of the polymerization reactor prior to injection of catalystcomposition, preparation of the stock solutions, propylenepolymerizations and product work up were performed as in Example 14. Theligands that were used are L4, L5 and L29 described above.

[0333] In situ preparation of metal-ligand compositions: Stock solutionswere prepared as follows: The “metal precursor solution” is a 10 mMsolution of Hf(NMe₂)₄ in toluene or a 10 mM solution of Zr(NMe₂)₄. The“ligand solutions” are 25 mM solutions of the representative ligands intoluene, prepared in an array of 1 mL glass vials by dispensing 0.030 mLof a 25 mM ligand solution in a 1 mL glass vial. To each 1 mL glass vialcontaining ligand/toluene solution was added 0.075 mL of the metalprecursor solution (0.75 μmol), to form the metal-ligand combinationsolution. The reaction mixtures we allowed to sit at 80° C. for 2-3hours during which time most of the solvent evaporates. The reactionmixtures were dried completely by blowing a stream of Argon over the 1mL vial. Prior to addition of alkylation and activator solution, a smallamount of solvent (0.020 mL) was added to the dry composition.

[0334] Injection of solutions into the pressure reactor vessel: To theligand metal composition, 0.037 mL of a 500 mM solution of 1-octene intoluene and 0.020 mL toluene and 0.112 mL of the group 13 reagentsolution was added to the 1 mL vial. After 9 minutes, 0.165 mL (0.083μmol) of the “activator solution” was added to the 1 mL vial. Aboutanother 30 seconds later, 0.090 mL of the 1 mL vial contents, followedimmediately by 0.310 mL of toluene, were injected into the reactionvessel. The results are described in table 24.

[0335] Polymerization: The polymerization reaction was allowed tocontinue for the 155-600 seconds, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The polymerization times were the lesser of the maximum desiredpolymerization reaction time or the time taken for a predeterminedamount of monomer gas to be consumed in the polymerization reaction. Thespecific times for each polymerization are shown in table 24. After thereaction time elapsed, the reaction was quenched by addition of anoverpressure of carbon dioxide.

[0336] Product work up: After the polymerization reaction, the glassvial insert, containing the polymer product and solvent, was removedfrom the pressure cell and removed from the inert atmosphere dry box,and the volatile components were removed using a centrifuge vacuumevaporator. After most of the volatile components had evaporated, thevial contents were dried thoroughly by evaporation at elevatedtemperature under reduced pressure. The vial was then weighed todetermine the yield of polymer product. The polymer product was thenanalyzed by rapid GPC, as described above to determine the molecularweight of the polymer produced, and by FTIR spectroscopy to determinecrystallinity. The results are described in table 24. TABLE 24 Resultsof examples 15.A and 15.F Polym. Melting Weight Temp. Metal time Cryst.point average Ligand (° C.) precursor (sec) Activity^(a) Index^(b) (°C.) % mmmm MW (k) A L4 75 Hf(NMe₂)₄ 301 372 0.77 141 73 845 B L5 75Hf(NMe₂)₄ 174 765 0.72 131 70 385 C L4 75 Zr(NMe₂)₄ 308 80 0.74 129 nd682 D L5 75 Zr(NMe₂)₄ 218 255 0.65 118 nd 517 E L29 75 Hf(NMe₂)₄ 155 4960.16 nd nd 288 F L29 75 Zr(NMe₂)₄ 600 18 0.19 nd nd 68

Example 16 Ethylene/l-Octene Copolymerization

[0337] Ten polymerization reactions were carried out with metal complexC 21 described above at different activation conditions, for thecopolymerization of ethylene and 1-octene.

[0338] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.10 mL of a 0.02 M solution of group 13reagents in toluene and 3.8 mL of toluene were injected into eachpressure reaction vessel through a valve. The temperature was then setto 130° C. and the stirring speed was set to 800 rpm, and the mixturewas exposed to ethylene at 100 psi pressure. An ethylene pressure of 100psi in the pressure cell and the temperature setting were maintained,using computer control, until the end of the polymerization experiment.The identity of the of group 13 reagents is described in table 25.

[0339] Preparation of the group 13 reagent, activator stock solutionsand metal complex solution: The “activator solution” is a 5 mM solutionof N,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution is either a 0.20 M solutionof triisobutylaluminium (“TIBA”) or 0.20 M solution of triethylaluminium(“TEAL”) or a 0.20 M solution of trimethylaluminium (“TMA”) or 0.20 Msolution of diisobutylaluminiumhydride (“DIBAL”) or a 0.20 M solution oftriethylboron (“BEt₃”), all “group 13 reagent” solutions were solutionsin toluene. The metal complex solution is 5 mM solution of C21 intoluene (27.5 mg of C21 dissolved in 6.4 mL toluene).

[0340] Activation and Injection of solutions into the pressure reactorvessel: First, 0.016 mL of a 0.5 M solution of 1-octene in toluene wasdispensed into a 1 mL vial. Then, 0.060 mL (1.2 μmol) of the group 13reagent solution was dispensed into the 1 mL vial as specified in thetable 25. Then, 0.080 ml (0.4 μmol) of the metal complex solution (5 mMin toluene) followed by 0.020 ml toluene was added to the 1 mL vial.After around 9 min, 0.420 mL 1-octene, followed immediately by 0.380 mLof toluene were injected into the reaction vessel. After another 30seconds, 0.088 mL (0.44 μmol) of the “activator solution” was added tothe 1 mL vial. After 30 seconds elapsed, a fraction of the total 1 mLvial contents (listed in table 25 as Catalyst injection fraction),followed immediately by approximately 0.7 mL of toluene, were injectedinto the reaction vessel. The array of experiments with values forequivalents and identity of group 13 reagent and injection fractions isdescribed in table 25.

[0341] Polymerization: The polymerization reaction was allowed tocontinue for the time shown in table 25A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide sent to the reactor.

[0342] Product work up: ethylene/1-octene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine 1 -ocetene incorporation. Results are presented in Table26-28. TABLE 25 Description of array of polymerization experiments forexamples 16.A.1.- 16.E.2. Polymerization 1 2 group 13 group 13 temp (°C.) 130 130 reagent^(a)) reagent^(b)) A C21 C21 30 TIBA TIBA B C21 C2130 DIBAL DIBAL C C21 C21 30 TMA TMA D C21 C21 30 TEAL TEAL E C21 C21 30BEt₃ BEt₃ Catalyst 0.5 0.25 injection fraction Activator ABF20 ABF20

[0343] TABLE 25A Polymerization times in seconds of examples16.A.1.-16.E.2. 1 2 A 350 457 B 278 349 C 311 457 D 169 466 E 601 600

[0344] TABLE 26 Activity (mg polymer per minute per μmol) of examples16.A.1.-16.E.2. 1 2 A 242 338 B 339 492 C 278 322 D 466 307 E 112 126

[0345] TABLE 27 wt % Octene incorporation of examples 16.A.1.-16.E.2. 12 A 38 32 B 40 36 C 38 33 D 32 33 E 43 37

[0346] TABLE 28 Weight average molecular weight (k) of examples16.A.1.-16.E.2. 1 2 A 51 71 B 50 67 C 58 78 D 50 72 E 380 793

Example 17 Propylene Polymerization using metal complex 7, 8, 9, 10 atdifferent polymerization temperatures.

[0347] In this example, thirty-one polymerization reactions were carriedout. The reactor was prepared as in Example 11, above. In addition, thepolymerization was run in the same manner and the polypropylene polymerwas worked up in the same manner as in Example 11, above.

[0348] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0349] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution is either a 0.2 M solutionof diisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”). All “group 13 reagent” solutions weresolutions in toluene.

[0350] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.2 M group 13 reagentsolution was dispensed into a 1 ml vial as specified in the table 29.0.100 mL (0.4 μmol) of the metal complex solution (4 mM in toluene) wasadded to the 1 mL vial. This mixture was held at at ambient temperaturefor a time period of t, as indicated in table 29. Then, 0.088 mL (0.44μmol) of the “activator solution” was added to the 1 mL vial. After thetime period t₂ elapsed (time listed in table 29), a fraction of thetotal 1 mL vial contents (listed in table 29), followed immediately byapproximately 0.3 mL of toluene, were injected into the reaction vessel.The array of experiments with values for equivalents of group 13reagent, t₁, t₂ and injection fraction is described in table 29.

[0351] Polymerization: The polymerization reaction was allowed tocontinue for the time shown in table 29A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide sent to the reactor.

[0352] Product work up: Propylene Polymerizations: This part of thisexample was performed as described in Example 11, above. The results arepresented in tables 30-32. TABLE 29 Description of polymerizationexperiments using complexes 7-10 (examples 17.A.1-17.H.3): group 13group 13 1 2 3 4 reagent^(a) reagent^(b) A C7 C7 C7 C7 30 DIBAL B C7 C7C7 C7 10 DIBAL C C8 C8 C8 C8 30 DIBAL D C8 C8 C8 C8 10 DIBAL E C9 C9 C9C9 30 DIBAL F C9 C9 C9 C9 10 DIBAL G C10 C10 C10 C10 30 DIBAL H C10 C10C10 10 DIBAL t₁ (min) 10 10 10 10 t₂ (min) 0.5 0.5 0.5 0.5 Injection0.15 0.15 0.15 0.45 Fraction Polym. 90 90 110 130 Temp. (° C.) group 13DIBAL TMA DIBAL DIBAL reagent^(c) Activator ABF20 ABF20 ABF20 ABF20

[0353] TABLE 29A Polymerization times in seconds for examples17.A.1.-17.H.3. 1 2 3 4 A 346 178 288 661 B 291 150 341 900 C 272 145266 902 D 251 141 367 902 E 159 182 170 383 F 159 157 195 528 G 172 169201 204 H 179 155 196

[0354] TABLE 30 Activity (mg polymer per minute per μmol) of examples17.A.1.-17.H.3. 1 2 3 4 A 316 1020 320 49 B 416 1287 277 32 C 399 1254348 19 D 489 1496 240 21 E 989 1016 624 78 F 1006 1304 524 55 G 848 1250518 145 H 754 1495 507

[0355] TABLE 31 Crystallinity index of examples 17.A.1.-17.H.3. 1 2 3 4A 0.91 0.87 0.84 0.88 B 0.88 0.88 0.89 0.89 C 0.86 0.82 0.84 0.83 D 0.850.82 0.84 0.86 E 0.86 0.86 0.86 0.88 F 0.85 0.83 0.84 0.87 G 0.83 0.860.86 0.91 H 0.87 0.87 0.85

[0356] TABLE 32 Weight average molecular weight (k) of examples17.A.1.-17.H.3. 1 2 3 4 A 536 350 161 32 B 552 310 175 50 C 579 422 21844 D 859 345 231 56 E 404 299 177 40 F 525 368 206 46 G 425 336 154 33 H604 361 186  3

Example 18 Propylene Polymerization using metal complex 11 (C11) atdifferent activation methods.

[0357] In this example, sixteen polymerization reactions were carriedout. The reactor was prepared as in Example 11, above. In addition, thepolymerization was run in the same manner and the polypropylene polymerwas worked up in the same manner as in Example 11, above.

[0358] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0359] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 2.5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution is either a 0.05 M solutionof triisobutylaluminium (“TIBA”) or 0.05 M solution of triethylaluminium(“TEAL”) or a 0.05 M solution of trimethylaluminium (“TMA”) or 0.05 Msolution of diisobutylaluminiumhydride (“DIBAL”) or a 0.05 M solution ofAkzo PMAO-IP (“PMAO”) or 0.05 M of Akzo MMAO-3A (“MMAO”), all “group 13reagent” solutions were solutions in toluene.

[0360] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.05 M group 13 reagentsolution was dispensed into a 1 mL vial that was kept at a constantpremix temperature as specified in the table 33. Then, 0.100 mL (0.25μmol) of the metal complex solution (2.5 mM in toluene) was added to the1 mL vial. This mixture was held at a premix temperature for a timeperiod of t₁ as indicated in table 33. Then, 0.110 mL (0.275 μmol) ofthe “activator solution” was added to the 1 mL vial. After the timeperiod t₂ elapsed, a fraction of the total 1 mL vial content, followedimmediately by approximately 0.3 mL of toluene, were injected into thereaction vessel. The array of experiments with values for equivalents ofgroup 13 reagent, t₁, t₂ and injection fraction is described in table33.

[0361] Polymerization: The polymerization reaction was allowed tocontinue for the time shown in table 33A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide sent to the reactor.

[0362] Product work up: Propylene Polymerizations: This part of thisexample was performed as described in Example 11, above. The results arepresented in tables 34-36.

[0363] The array of experiments is described in table 33. The specifictimes for each polymerization are shown in table 33a. The results arepresented in tables 34-36. TABLE 33 Description of polymerizationexperiments using complex 11 (examples 18.A.1-18.H.2): group 13 group 131 2 reagent^(a)) reagent^(b)) A C 11 C 11 6 TIBA TIBA B C 11 C 11 6 TEALTEAL C C 11 C 11 6 TMA TMA D C 11 C 11 10 TMA TMA E C 11 C 11 6 DIBALDIBAL F C 11 C 11 10 DIBAL DIBAL G C 11 C 11 6 PMAO-IP PMAO-IP H C 11 C11 6 MMAO MMAO Injection Fraction 0.132 0.132 Polym. Temp. (° C.) 110110 T₁ (min) 10 0.5 T₂ (min) 0.5 0.5 Premix Temp. (° C.) 25 25 ActivatorABF20 ABF20

[0364] TABLE 33A Polymerization times in seconds for examples18.A.1.-18.H.2. 1 2 A 241 279 B 236 199 C 263 226 D 303 223 E 257 601 F242 601 G 199 231 H 232 186

[0365] TABLE 34 Activity (mg polymer per minute per μmol) of examples18.A.1.-18.H.2. 1 2 A 782 577 B 741 959 C 663 794 D 533 831 E 714 224 F714 160 G 930 842 H 741 1050

[0366] TABLE 35 Crystallinity index of examples 18.A.1.-18.H.2. 1 2 A0.87 0.88 B 0.87 0.87 C 0.87 0.86 D 0.86 0.88 E 0.89 0.85 F 0.87 0.84 G0.89 0.81 H 0.88 0.84

[0367] TABLE 36 Weight average molecular weight (k) of examples18.A.1.-18.H.2. 1 2 A 80 81 B 86 94 C 101 105 D 101 n.d. E 77 n.d. F 7570 G 109 n.d. H 107 106

Example 19 Propylene Polymerization using metal complex 1, 2, 9, 12, 13,14, 15 and 16.

[0368] In this example, eight polymerization reactions were carried out.The reactor was prepared as in Example 11, above.

[0369] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0370] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution a 0.2 M solution oftrimethylaluminium (“TMA”), all “group 13 reagent” solutions weresolutions in toluene.

[0371] Activation and Injection of solutions into the pressure reactorvessel: First, 0.120 mL (0.6 μmol) of the metal complex solution (5 mMin toluene) was added to the 1 mL vial. Then, 0.012 ml of a 0.5 Msolution of 1-octene intoluene followed by 0.090 ml of the 0.2 M group13 reagent solution was dispensed into a 1 mL as specified in the table37. This mixture was held for a time period of t₁ as indicated in table37. Then, 0.132 mL (0.66 μmol) of the “activator solution” was added tothe 1 mL vial. After the time period t₂ elapsed (time listed in table37), a fraction of the total 1 mL vial contents (listed in table 37),followed immediately by approximately 0.3 mL of toluene, were injectedinto the reaction vessel. The array of experiments with values forequivalents of group 13 reagent, t₁, t₂ and injection fraction isdescribed in table 37.

[0372] Polymerization: The polymerization reaction was allowed tocontinue for the time shown in table 37A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide sent to the reactor.

[0373] Product work up: Propylene Polymerizations: This part of thisexample was performed as described in Example 11, above. The results arepresented in tables 38-40. TABLE 37 Description of polymerizationexperiments using complexes 1, 2, 9, 12, 13, 14, 15 and 16 (examples19.A.1-19.H.1): 1 Group 13 reagent^(b)) A C 13 TMA B C 14 TMA C C 15 TMAD C 16 TMA E C 12 TMA F C  9 TMA G C  1 TMA H C  2 TMA InjectionFraction 0.10 Polym. Temp. (° C.) 110 Group 13 reagent^(a)) 30 TMA t₁(min) 10 t₂ (min) 0.5 Activator ABF20

[0374] TABLE 37A Polymerization times in seconds for examples19.A.1-19.H.1. 1 A 431 B 224 C 900 D 900 E 94 F 174 G 165 H 86

[0375] TABLE 38 Activity (mg polymer per minute per μmol) of examples19.A.1-19.H.1. 1 A 230 B 716 C 79 D 47 E 2511 F 825 G 779 H 1466

[0376] TABLE 39 Crystallinity index of examples 19.A.1-19.H.1. 1 A 0.38B 0.56 C 0.53 D 0.30 E 0.92 F 0.91 G 0.88 H 0.88

[0377] TABLE 40 Weight average molecular weight (k) of examples19.A.1-19.H.1. 1 A 64 B 94 C 67 D 76 E 86 F 100 G 90 H 89

Example 20 Propylene Polymerization using metal complexes 9 and 12 atdifferent polymerization temperatures

[0378] In this example, four polymerization reactions were carried out.

[0379] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0380] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The “group 13 reagent” solution a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”), all “group 13 reagent” solutionswere solutions in toluene.

[0381] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.2 M group 13 reagentsolution was dispensed into a 1 mL vial as specified in the table 41.0.120 mL (0.6 μmol) of the metal complex solution (5 mM in toluene) wasadded to the 1 mL vial. This mixture was held at a premix temperaturefor a time period of tas indicated in table 41. Then, 0.132 mL (0.66μmol) of the “activator solution” was added to the 1 mL vial. After thetime period t₂ elapsed (time listed in table 41), a fraction of thetotal 1 mL vial contents (listed in table 41), followed immediately byapproximately 0.3 mL of toluene, were injected into the reaction vessel.The array of experiments with values for equivalents of group 13reagent, t1, t2 and injection fraction is described in table 41.

[0382] Polymerization: The polymerization reaction was allowed tocontinue for 120-900 seconds, during which time the temperature andpressure were maintained at their pre-set levels by computer control.The specific times for each polymerization are shown in table 41a. Afterthe reaction time elapsed, the reaction was quenched by addition of anoverpressure of carbon dioxide sent to the reactor.

[0383] Product work up: Propylene Polymerizations: This part of thisexample was performed as described in Example 11, above. The results arepresented in tables 42-45 TABLE 41 Description of polymerizationexperiments using complexes 9 and 12 (examples 20.A.1-20.B.2): group 13group 13 1 2 reagent^(a)) reagent^(b)) A C 9 C 9 30 DIBAL DIBAL B C 12 C12 30 DIBAL DIBAL Injection Fraction 0.075 0.20 Polym. Temp. (° C.) 110130 T₁ (min) 10 10 T₂ (min) 0.5 0.5 Activator ABF20 ABF20

[0384] TABLE 41A Polymerization times in seconds for examples20.A.1-20.B.2 1 2 A 215 900 B 120 901

[0385] TABLE 42 Activity (mg polymer per minute per μmol) of examples20.A.1-20.B.2 1 2 A 603 37 B 1232 49

[0386] TABLE 43 Crystallinity index of examples 20.A.1-20.B.2 1 2 A 0.860.86 B 0.83 0.78

[0387] TABLE 44 Melting points of examples (in ° C.) 20.A.1-20.B.2 1 2 A145/152 138/147 B 137/144 133/141

[0388] TABLE 45 Weight average molecular weight (k) of examples20.A.1-20.B.2 1 2 A 94 26 B 59 15

Example 21 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

[0389] Twenty-four polymerization reactions were carried out withdifferent ligand/metal compositions, different temperatures, activatorsand activation conditions for the polymerization of propylene. Ligands6-13, whose structures and synthesis are shown above, are used in thisexample.

[0390] In situ preparation of metal-ligand compositions: This part ofthis example was performed as described in Example 14, above.

[0391] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0392] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”).

[0393] Injection of solutions into the pressure reactor vessel: To theligand metal composition, 0.030 mL of a 500 mM solution of 1-octene intoluene and 0.028 ml of toluene and 0.112 mL of the group 13 reagentsolution was added to the 1 mL vial. After 9 minutes, 0.165 mL (0.83μmol) of the “activator solution” was added to the 1 mL vial. Aboutanother 30 seconds later, a fraction of the total 1 mL vial contents(listed in table 46 as Injection fractio), followed immediately byapproximately 0.3 mL of toluene, were injected into the reaction vessel.The array of experiments is described in detail in table 46.

[0394] Propylene Polymerizations and Product work up: This part of thisexample was performed as described in Example 11, above, with specificpolymerization times shown in table 51A. Results are presented in thetables 47-50.

[0395] Propylene Polymerizations and Product work up: This part of thisexample was performed as described in Example 11, above, with specificpolymerization times shown in table 46A. Results are presented in thetables 47-50. TABLE 46 Description of array of polymerizationexperiments for examples 21.A.1.-21.H.3. 1 2 3 A L10 L10 L10 B L11 L11L11 C L12 L12 L12 D L13 L13 L13 E L6  L6  L6  F L7  L7  L7  G L8  L8 L8  H L9  L9  L9  group 13 reagent^(a)) 30 DIBAL 30 DIBAL 30 DIBAL group13 reagent^(b)) DIBAL DIBAL DIBAL Activator ABF20 ABF20 ABF20 Polym.Temp (° C.): 90 110 130 Injection fraction 0.086 0.13 0.26

[0396] TABLE 46A Polymerization times in seconds of examples21.A.1.-21.H.3. 1 2 3 A 901 901 901 B 900 901 901 C 900 901 900 D 901901 901 E 252 327 901 F 359 902 901 G 288 287 900 H 155 229 900

[0397] TABLE 47 Activity (mg polymer per minute per μmol) of examples21.A.1.-21.H.3. 1 2 3 A 12 3 1 B 10 2 1 C 1 1 0 D 23 6 2 E 429 158 18 F250 50 10 G 329 191 15 H 853 258 20

[0398] TABLE 48 Crystallinity index of examples examples 21.A.1.-21.H.3.1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C n.d. n.d. n.d. D 0.74 n.d.n.d. E 0.85 0.84 0.81 F 0.89 0.84 0.86 G 0.84 0.87 0.82 H 0.80 0.86 0.84

[0399] TABLE 49 Weight average molecular weight (k) of examples21.A.1.-21.H.3. 1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C n.d. n.d. n.d.D 310 n.d. n.d. E 681 165 30 F 537 106 19 G 560 124 25 H 458 124 26

[0400] TABLE 50 Melting points of selected examples (in ° C.) 21.E.1.,21.F.1. and 21.H.1. 1 2 3 A B C D E 142/147 F 148 G H 146

Example 22 Preparation of Ligand/Metal Compositions and PropylenePolymerization with Ligand/Metal Compositions

[0401] Eighteen polymerization reactions were carried out with differentligand/metal compositions, different temperatures, activators andactivation conditions for the polymerization of propylene. LigandsL14-L19, whose structures and synthesis are shown above, are used inthis example.

[0402] In situ preparation of metal-ligand compositions: This part ofthis example was performed as described in Example 14, above.

[0403] Preparation of the polymerization reactor prior to injection ofcatalyst composition: This part of this example was performed asdescribed in Example 11, above.

[0404] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to 20 approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”).

[0405] Injection of solutions into the pressure reactor vessel: To theligand metal composition, 0.030 mL of a 500 mM solution of 1-octene intoluene and 0.112 mL of the group 13 reagent solution was added to the 1mL vial. After 9 minutes, 0.165 mL (0.83 μmol) of the “activatorsolution” was added to the 1 mL vial. About another 30 seconds later, afraction of the total 1 mL vial contents (listed in table 51), followedimmediately by approximately 0.3 mL of toluene, were injected into thereaction vessel. The array of experiments is described in detail intable 51.

[0406] Propylene Polymerizations and Product work up: This part of thisexample was performed as described in Example 11, above, with specificpolymerization times shown in table 51A. Results are presented in thetables 52-55. TABLE 51 Description of array of polymerizationexperiments for examples 22.A.1.-22.F.3. 1 2 3 A L14 L14 L14 B L15 L15L15 C L16 L16 L16 D L17 L17 L17 E L18 L18 L18 F L19 L19 L19 Polym. Temp(° C.): 90 110 130 group 13 reagent ^(a)) 30 DIBAL 30 DIBAL 30 DIBALgroup 13 reagent ^(b)) DIBAL DIBAL DIBAL Activator ABF20 ABF20 ABF20Injection fraction 0.065 0.13 0.26

[0407] TABLE 51A Polymerization times in seconds of examples22.A.1.-22.F.3. 1 2 3 A 900 902 901 B 901 901 900 C 224 290 901 D n.d.902 901 E 518 901 901 F 538 901 901

[0408] TABLE 52 Activity (mg polymer per minute per μmol) of examples22.A.1.-22.F.3. 1 2 3 A 2 1 1 B 9 2 1 C 556 188 14 D n.d. 1 1 E 203 33 6F 195 21 6

[0409] TABLE 53 Crystallinity index of examples examples 22.A.1.-22.F.3.1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C 0.48 0.52 0.47 D n.d. n.d.n.d. E 0.54 0.56 n.d. F 0.60 0.61 n.d.

[0410] TABLE 54 Weight average molecular weight (k) of examples22.A.1.-22.F.3. 1 2 3 A n.d. n.d. n.d. B n.d. n.d. n.d. C 334 97 18 Dn.d. n.d. n.d. E 229 62 n.d. F 248 46 n.d.

[0411] TABLE 55 Melting points (in ° C.) of selected examples for22.A.1.-22.F.3. 1 2 3 A B C 118 D E 130/139 F 134/141

Example 23 Ethylene-Styrene Copolymerization using metal complexes 7, 8,9 and 10 (C7, C8, C9, C10) at different activation conditions

[0412] Twenty-four polymerization reactions were run with differentmetal complexes, temperatures, activators and activating conditions forcopolymerization of ethylene and styrene.

[0413] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.10 mL of a 0.02 M group 13 reagent solutionin toluene and 3.8 mL of toluene were injected into each pressurereaction vessel through a valve. The identity of the group 13 reagentsolution is given in table 56. The temperature was then set to theappropriate polymerization temperature (as described in table 56), andthe stirring speed was set to 800 rpm, and the mixture was exposed toethylene at 100 psi pressure. An ethylene pressure of 100 psi in thepressure cell and the temperature setting were maintained, usingcomputer control, until the end of the polymerization experiment.

[0414] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is either a 0.2 M solution ofdiisobutylaluminiumhydride (“DIBAL”) or a 0.2 M solution oftrimethylaluminium (“TMA”), both in toluene.

[0415] Activation and Injection of solutions into the pressure reactorvessel: First, an appropriate amount of the 0.2 M group 13 reagentsolution was dispensed in a 1 mL vial which was kept at a constantpremix temperature as specified in the table 56. Then 0.100 mL of themetal complex solution (4 mM in toluene) was added. This mixture washeld at a premix temperature for a time t₁ as indicated in table 56,during which time, 0.420 mL of styrene followed immediately by 0.380 mLof toluene, were injected into the prepressurized reaction vessel. Then,0.088 mL (0.55 μmol) of the “activator solution” was added to the 1 mLvial. After the time period t₂ elapsed, a fraction (as indicated intable 56) of the total 1 mL vial contents, followed immediately byapproximately 0.3 mL of toluene were injected into the reaction vessel.The array of experiments is described in table 56.

[0416] Polymerization: The polymerization reaction was allowed tocontinue for the the time shown in table 56A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide.

[0417] Product work up: ethylene/styrene copolymerizations After thepolymerization reaction, the glass vial insert, containing the polymerproduct and solvent, was removed from the pressure cell and removed fromthe inert atmosphere dry box, and the volatile components were removedusing a centrifuge vacuum evaporator. After most of the volatilecomponents had evaporated, the vial contents were dried thoroughly byevaporation at elevated temperature under reduced pressure. The vial wasthen weighed to determine the yield of polymer product. The polymerproduct was then analyzed by rapid GPC, as described above to determinethe molecular weight of the polymer produced, and by FTIR spectroscopyto determine the styrene incorporation. Results are presented in thetables 57-59. TABLE 56 Description of polymerization experiments usingcomplexes 7-10 for examples 23.A.1-23.H.3. 1 2 3 group 13 reagent^(a)) AC 7 C 7 C 7 30 B C 7 C 7 C 7 10 C C 8 C 8 C 8 30 D C 8 C 8 C 8 10 E C 9C 9 C 9 30 F C 9 C 9 C 9 10 G C 10 C 10 C 10 30 H C 10 C 10 C 10 10Injection Fraction  0.25  0.25  0.25 Polym. Temp. (° C.) 110 110 110Premix temp. (° C.)  24  50  50 group 13 reagent^(c) DIBAL DIBAL TMAgroup 13 reagent^(b)) DIBAL DIBAL TMA Activator ABF20 ABF20 ABF20

[0418] TABLE 56A Polymerization times in seconds for examples23.A.1.-23.H.3. 1 2 3 A 720 337 305 B 901 749 900 C 353 259 284 D 900840 902 E 760 265 281 F 902 901 901 G 582 300 492 H 902 902 883

[0419] TABLE 57 Activity (mg polymer per minute per μmol) of examples23.A.1.-23.H.3. 1 2 3 A 186 386 453 B 129 180 126 C 346 457 413 D 122155 117 E 188 524 492 F 127 139 129 G 244 467 276 H 125 144 143

[0420] TABLE 58 Styrene incorporation (mol %) of examples23.A.1.-23.H.3. 1 2 3 A 3.1 3.7 3.6 B 3.8 4.5 4.9 C 2.5 3.1 2.9 D 2.83.6 3.7 E 3.5 4.1 3.5 F 3.9 4.6 4.4 G 3.1 3.8 3.3 H 3.9 4.8 4.3

[0421] TABLE 59 Weight average molecular weight (k) of examples23.A.1.-23.H.3. 1 2 3 A 322 255 311 B 512 571 987 C 334 253 233 D 530384 577 E 645 270 274 F 464 652 762 G 301 214 256 H 176 512 743

Example 24 Ethylene-Styrene Copolymerization using metal complexes 17,18, 19 10 and 20 (C17, C18, C19, C20) at different activation conditions

[0422] Sixteen polymerization reactions were run with different metalcomplexes and activating conditions for copolymerization of ethylene andstyrene.

[0423] Preparation of the polymerization reactor prior to injection ofcatalyst composition: A pre-weighed glass vial insert and disposablestirring paddle were fitted to each reaction vessel of the reactor. Thereactor was then closed, 0.050 mL of a 0.02 M group 13 reagent solutionin toluene and 4.55 mL of toluene were injected into each pressurereaction vessel through a valve. The identity of the group 13 reagentsolution is given in table 60. The temperature was then set to 110° C.,and the stirring speed was set to 600 rpm, and the mixture was exposedto ethylene at 100 psi pressure. An ethylene pressure of 100 psi in thepressure cell and the temperature setting were maintained, usingcomputer control, until the end of the polymerization experiment.

[0424] Preparation of the group 13 reagent and activator stocksolutions: The “activator solution” is a 5 mM solution ofN,N′-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene(“ABF20”). The solution is heated to approximately 85° C. to dissolvethe reagent. The group 13 reagent solution is a 0.2 M solution oftriisobutylaluminium (“TIBA”).

[0425] Activation and Injection of solutions into the pressure reactorvessel: First, 0.200 mL of the metal complex solution (5 mM in toluene)was dispensed in a 1 mL vial. Then, an appropriate amount of the 0.2 Mgroup 13 reagent solution was added. This mixture was held for 75seconds, during which time, 0.500 mL of styrene followed immediately by0.500 mL of toluene, and 0.100 mL of the “activator solution” followedimmediately by 0.400 mL of toluene were injected into the prepressurizedreaction vessel. Then, half of the total 1 mL vial contents, followedimmediately by approximately 0.3 mL of toluene were injected into thereaction vessel. The array of experiments is described in table 60.

[0426] Polymerization: The polymerization reaction was allowed tocontinue for the times shown in table 60A, during which time thetemperature and pressure were maintained at their pre-set levels bycomputer control. The polymerization times were the lesser of themaximum desired polymerization reaction time or the time taken for apredetermined amount of monomer gas to be consumed in the polymerizationreaction. After the reaction time elapsed, the reaction was quenched byaddition of an overpressure of carbon dioxide.

[0427] Product work up: ethylene/styrene copolymerizations: This part ofthis example was performed as described in example 23. Results arepresented in the tables 61-63. TABLE 60 Description of polymerizationexperiments using complexes 7-10 (examples 24.A.1-24.H.2): 1 2 A C 17 C17 B C 17 C 17 C C 18 C 18 D C 18 C 18 E C 19 C 19 F C 19 C 19 G C 20 C20 H C 20 C 20 Polym. Temp. (° C.) 110 110 group 13 reagent^(c) 5 TIBA10 TIBA group 13 reagent^(b)) TIBA TIBA Activator ABF20 ABF20

[0428] TABLE 60A Polymerization times in seconds for examples24.A.1-24.H.2 1 2 A 900 900 B 900 900 C 900 900 D 900 900 E 639 408 F670 464 G 900 743 H 900 797

[0429] TABLE 61 Activity (mg polymer per minute per μmol) of examples24.A.1-24.H.2 1 2 A 21 23 B 22 22 C 20 23 D 21 22 E 43 61 F 41 57 G 2844 H 29 41

[0430] TABLE 62 Styrene incorporation (mol %) of examples 24.A.1-24.H.21 2 A 3.1 3.3 B 3.2 3.4 C 4.3 3.6 D 3.6 3.8 E 3.9 3.3 F 4.1 3.3 G 5.54.7 H 5.2 5.1

[0431] TABLE 63 Weight average molecular weight (k) of examples24.A.1-24.H.2 1 2 A 50 42 B 62 36 C 79 34 D 80 47 E 118 49 F 116 52 G549 259 H 422 226

[0432] It is to be understood that the above description is intended tobe illustrative and not restrictive. Many embodiments will be apparentto those of skill in the art upon reading the above description. Thescope of the invention should, therefore, be determined not withreference to the above description, but should instead be determinedwith reference to the appended claims, along with the full scope ofequivalents to which such claims are entitled. The disclosures of allarticles and references, including patent applications and publications,are incorporated herein by reference for all purposes.

What is claimed is:
 1. A process for the polymerization of monomers,said process employing a composition comprising: (1) a ligandcharacterized by the following general formula:

wherein Ris selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl and combinationsthereof. T is —CR²R³— and R² are R³ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof,R⁴, R⁵, R⁶ and R⁷ are each independently selected from the groupconsisting of is hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may bejoined together in a ring structure; provided that either R³ or R⁷ isselected only from the group consisting of aryl, substituted aryl,heteroaryl and substituted heteroaryl; (2) a metal precursor compoundcharacterized by the general formula Hf(L)_(n), wherein each L isindependently selected from the group consisting of halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof or optionally two or more L groups are joined intoa ring structure; n is 1, 2, 3, 4, 5, or 6; and (3) optionally, at leastone activator.
 2. The process of claim 1, wherein said ligand ischaracterized by the general formula:

such that E is carbon and wherein Q¹, Q², Q³, Q⁴ and Q⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, andcombinations thereof; optionally two of Q², Q³ and Q⁴ are joinedtogether in a ring structure.
 3. The process of claim 1, wherein saidligand is characterized by the general formula:

wherein R¹⁰, R¹¹, R¹² and R¹³ are each independently selected from thegroup consisting of hydrogen, halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms;and R¹⁴ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.
 4. The process of claim 3, wherein said ligandis characterized by the formula:

wherein Q¹, Q², Q³, Q⁴ and Q⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally two of Q², Q³ and Q⁴ are joined together in a ring structure.5. A process for the polymerization of monomers, said process employinga metal-ligand complex characterized by the following formula:

wherein R¹ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl and combinationsthereof. T is —CR²R³— and R² are R³ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;R⁴, R⁵, R⁶ and R⁷ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may bejoined together in a ring structure; provided that either R³ or R⁷ isselected only from the group consisting of aryl, substituted aryl,heteroaryl and substituted heteroaryl; each L is independently selectedfrom the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof oroptionally two or more L groups are joined into a ring structure; n is1, 2, 3, 4, 5, or 6; and x is 1 or
 2. 6. The process of claim 5, whereinsaid metal complex is characterized by the formula:

wherein Q¹, Q², Q³, Q⁴ and Q⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally two of Q², Q³ and Q⁴ are joined together in a ring structure;and x=1.
 7. The process of claim 5, wherein said complex ischaracterized by the formula:

wherein R¹⁰, R¹¹, R¹² and R¹³ are each independently selected from thegroup consisting of hydrogen, halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms;and R¹⁴ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof; and x=1.
 8. The process of claim 7, whereinsaid complex is characterized by the general formula:

wherein Q¹, Q², Q³, Q⁴ and Q⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally two of Q², Q³ and Q⁴ are joined together in a ring structure.9. A process for the polymerization of monomers, said process employinga metal complex characterized by the formula:

where M is zirconium or hafnium; wherein R¹ is selected from the groupconsisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl,substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl and combinations thereof. T is a bridging groupselected group consisting of —CR²R³— and —SiR²R³— with R² and R³ beingindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof; J′″ being selected from the group ofsubstituted heteroaryls with 2 atoms bonded to the metal M, at least oneof those 2 atoms being a heteroatom, and with one atom of J′″ is bondedto M via a dative bond, the other through a covalent bond; and L¹ and L²are independently selected from the group consisting of halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof or optionally two or more L groups are joined intoa ring structure.
 10. The process of claim 9, wherein said complex ischaracterized by the formula:

wherein each of R⁴, R⁵ and R⁶ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may bejoined together in a ring structure; and E″ is either carbon or nitrogenand is part of a cyclic aryl, substituted aryl, heteroaryl, orsubstituted heteroaryl group.
 11. The process of claim 10, wherein saidcomplex is characterized by the formula:

wherein R¹⁰, R¹¹, R¹² and R¹³ are each independently selected from thegroup consisting of hydrogen, halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.12. The process of claim 11, wherein said complex is characterized bythe formula:

as wherein Q¹, Q², Q³, Q⁴ and Q⁵ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof; oroptionally, two of Q², Q³ and Q⁴ are joined together in a ringstructure.
 13. The process of either of claims 1,3,5,7,9,10 or 11,wherein R¹ is characterized by the general formula:

wherein E is either carbon or nitrogen, Q¹ and Q⁵ are substituents onthe R¹ ring at a position ortho to E, with Q¹ and Q⁵ being independentlyselected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl,but provided that Q¹ and Q⁵ are not both methyl; and Q″_(q) representsadditional possible substituents on the ring, with q being 1, 2, 3, 4 or5 and Q′ being selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.
 14. The process of either of claims 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein said process employs at leastone activator.
 15. The process of claim 14 wherein said at least oneactivator comprises an ion forming activator and another reagentselected from the group consisting of a group 13 reagent, a divalentreagent and an alkali metal reagent.
 16. The process of either of claims1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein said process employs atleast one monomer that is an olefin, diolefin or unsaturated compound.17. The process of claim 16, wherein there are at least 2 monomers. 18.The process of claim 17, wherein said at least 2 monomers compriseethylene and an α-olefin.
 19. The process of claim 17, wherein said atleast 2 monomers comprise ethylene and either 1-octene or 1-hexene. 20.The process of claim 17, wherein there are at least 3 monomers in theprocess, with said monomers comprising ethylene, an α-olefin and adiolefin.
 21. The process of claim 17, wherein said two monomerscomprise ethylene and 1-octene.
 22. The process of claim 21, wherein R³is either aryl or substituted aryl.
 23. The process of claim 21, whereinR¹ is selected from the group consisting of mesityl; 2-Me-naphthyl;2,6-(Pr^(i))₂-C₆H₃—; 2-Pr¹-6-Me-C₆H₃—2,6-Et₂-C₆H₃—; and2-sec-butyl-6-Et-C₆H₃—.
 24. The process of claim 21, wherein, whenpresent, R⁷ is selected from the group consisting of phenyl, napthyl,mesityl, anthracenyl and phenanthrenyl.
 25. A catalyst for theproduction of a polymer comprising a composition comprising: (1) aligand characterized by the following general formula:

wherein R¹ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl and combinationsthereof. T is —CR²R³— and R² are R³ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;R⁴, R⁵, R⁶ and R⁷ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof,and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may bejoined together in a ring structure; provided that either R³ or R⁷ isselected only from the group consisting of aryl, substituted aryl,heteroaryl and substituted heteroaryl; (2) a metal precursor compoundcharacterized by the general formula Hf(L)_(n) wherein each L isindependently selected from the group consisting of halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof or optionally two or more L groups are joined intoa ring structure; n is 1, 2, 3, 4, 5, or 6; and (3) optionally, at leastone activator.
 26. A catalyst for the production of a polymer comprisingat least one activator and a metal-ligand complex characterized by thefollowing formula:

wherein R¹ is selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl and combinationsthereof. T is —CR²R³— and R² are R³ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;R⁴, R⁵, R⁶ and R⁷ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;and optionally, any combination of R¹, R², R³, R⁴, R⁵, or R⁶ may bejoined together in a ring structure; provided that either R³ or R⁷ isselected only from the group consisting of aryl, substituted aryl,heteroaryl and substituted heteroaryl; each L is independently selectedfrom the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, ethers, thioethers and combinations thereof oroptionally two or more L groups are joined into a ring structure; n is1, 2, 3, 4, 5, or 6; and x is 1 or
 2. 27. A catalyst for the productionof a polymer comprising at least one activator and a metal complexcharacterized by the formula:

where M is zirconium or hafnium; wherein R¹ is selected from the groupconsisting of alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl,substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl and combinations thereof. T is a bridging groupselected group consisting of —CR²R³— and —SiR²R³— with R² and R³ beingindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof; J′″ being selected from the group ofsubstituted heteroaryls with 2 atoms bonded to the metal M, at least oneof those 2 atoms being a heteroatom, and with one atom of J′″ is bondedto M via a dative bond, the other through a covalent bond; and L¹ and L²are independently selected from the group consisting of halide, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, ethers, thioethers andcombinations thereof or optionally two or more L groups are joined intoa ring structure.
 28. The catalyst of either of claims 25, 26 or 27,wherein R¹ is characterized by the general formula:

wherein E is either carbon or nitrogen, Q¹ and Q⁵ are substituents onthe R¹ ring at a position ortho to E, with Q¹ and Q⁵ are independentlyselected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl,but provided that Q¹ and Q⁵ are not both methyl; and Q″_(q) representsadditional possible substituents on the ring, with q being 1, 2, 3, 4 or5 and Q″ being selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.
 29. The catalyst of either of claims 25, 26 or27, wherein R³ is selected from the group consisting of benzyl, phenyl,naphthyl, 2-biphenyl, 2-dimethylaminophenyl, 2-methoxyphenyl,anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl, andphenanthrenyl.
 30. The catalyst of either of claim 28, wherein Q¹ and Q⁵are, independently, selected from the group consisting of —CH₂R¹⁵,—CHR¹⁶R¹⁷ and methyl, provided that not both Q¹ and Q⁵ are methyl,wherein R¹⁵ is selected from the group consisting of alkyl, substitutedalkyl, aryl and substituted aryl; R¹⁶ and R¹⁷ are independently selectedfrom the group consisting of alkyl, substituted alkyl, aryl andsubstituted aryl; and optionally R¹⁶ and R¹⁷ are joined together in aring structure having from 3-50 non-hydrogen atoms.
 31. The catalyst ofclaim 29, wherein Q², Q³, and Q⁴ are each hydrogen and Q¹ and Q⁵ areboth isopropyl; or both ethyl; or both sec-butyl; or Q¹ is methyl and Q⁵is isopropyl; or Q¹ is ethyl and Q⁵ is sec-butyl.
 32. The catalyst ofclaim 28, wherein R¹ is selected from the group consisting of mesityl;2-Me-naphthyl; 2,6-(Pr¹)₂-C₆H₃—; 2-Pr¹6-Me-C₆H₃—; 2,6-Et₂-C₆H₃—; and2-sec-butyl-6-Et-C₆H₃—.
 33. The catalyst of either of claims 25, 26 or27, wherein R⁷ is selected from the group consisting of phenyl, napthyl,mesityl, anthracenyl and phenanthrenyl.